Materials, methods, and uses for photochemical generation of acids and/or radical species

ABSTRACT

The present invention provides compounds and compositions, which include: at least one chromophore having strong simultaneous two-photon or multi-photon absorptivity; at least one acid- or radical-generator in close proximity to the chromophore; such that the single- or multi-photon excitation of the chromophore results in the generation of an acid and/or redical that is capable of activating chemistry; and such that compositions of matter based on the componds and compositions of the invention can be photo-patterned by one- or multiphoton excitation.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.60/280,672, filed Mar. 30, 2001, the entire contents of which are herebyincorporated by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

The invention was partially supported by the United States Governmentthrough the National Science Foundation (Grant No. CHE9408701) and theOffice of Naval Research (ONR Grant No. N00014-95-1-1319).

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to compositions and compounds that have largetwo-photon or higher-order absorptivities, which, after excitation,generate Lewis or Brønsted acids, radicals or a combination thereof Theinvention also relates to methods of making and using the compositionsand compounds.

2. Discussion of the Background

Two-photon or higher-order absorption refers to the initial simultaneousabsorption of two or more photons (also referred to as multi-photonabsorption) without the actual population of an excited state by theabsorption of a single photon.

Molecular two-photon absorption was predicted in Göppert-Mayer, M., Ann.Phys. 1931, 9, 273. Upon the invention of pulsed ruby lasers in 1960,experimental observation of two-photon absorption became reality. In theyears since, multi-photon excitation has found application in biologyand optical data storage, as well as in other fields.

Although interest in multi-photon excitation has exploded, there is apaucity of two-photon absorbing dyes with adequately strong two-photonabsorption in the correct spectral region for many applications.

There are two key advantages of two-photon (or higher-order) inducedprocesses relative to single-photon induced processes. Whereassingle-photon absorption scales linearly with the intensity of theincident radiation, two-photon absorption scales quadratically.Higher-order absorptions will scale with yet a higher power of incidentintensity. As a result, it is possible to perform multi-photon inducedprocesses with three dimensional spatial resolution. Further, becausethese processes involve the simultaneous absorption of two or morephotons, the chromophore is excited with a number of photons whose totalenergy equals the energy of a multi-photon absorption transition,although each photon individually has insufficient energy to excite thechromophore. Because the exciting light is not attenuated bysingle-photon absorption in this case, it is possible to exciteselectively molecules at a greater depth within a material than would bepossible via single-photon excitation by use of a beam that is focusedto that depth in the material. These two advantages also apply to, forexample, excitation within tissue or other biological materials. Inmulti-photon lithography or stereolithography, the nonlinear scaling ofabsorption with intensity can lead to the ability to write features of asize below the diffraction limit of light, and the ability to writefeatures in three dimensions, which is also of interest for holography.

The ability to realize many of the possible applications of two-photonor higher-order absorption by molecules rests on the availability ofchromophores with large two-photon or higher-order absorption crosssections. We have taught in U.S. Pat. No. 6,267,913, which isincorporated herein by reference, that certain classes of moleculesexhibit enhanced two-photon or multi-photon absorptivities. Thesemolecules can be categorized as follows:

-   -   a) molecules in which two donors are connected to a conjugated        π-electron bridge (abbreviated “D-π-D” motif);    -   b) molecules in which two donors are connected to a conjugated        π-electron bridge which is substituted with one or more electron        accepting groups (abbreviated “D-A-D” motif);    -   c) molecules in which two acceptors are connected to a        conjugated π-electron bridge (abbreviated “A-π-A” motif); and    -   d) molecules in which two acceptors are connected to a        conjugated π-electron bridge which is substituted with one or        more electron donating groups (abbreviated “A-D-A” motif).

Accordingly, molecules from the aforementioned classes can be excitedefficiently by simultaneous two-photon (or higher-order) absorption,leading to efficient generation of electronically excited states. Theseexcited state species can be exploited in a great variety of chemicaland physical processes, with the advantages enabled by multiphotonexcitation. For example, by employing polymerizable resin formulationscontaining cross-linkable acrylate containing monomers and D-π-Dmolecules as two-photon initiators of radical polymerization, complexthree-dimensional objects can be prepared using patterned two-photonexcitation. Most two-photon induced photopolymerization processesinvolve radical reactions in which there is some volume decrease uponpolymerization (Cumpston et al. Nature 398, (1999) 51; Belfield, K. D.et al. J. Am. Chem. Soc. 122, (2000) 1217).

The applications that depend upon two-photon or multi-photon excitationalso require that the two-photon or multiphoton excited states cause achemical or physical change in the exposed region of the materials. Suchchanges can result from the generation of a Brønsted or Lewis acidand/or radical species and subsequent further reactions of that specieswith other components in the material, for example, resulting incleavage of a functional group from a polymer or initiation of apolymerization, as is well known to one skilled in the art oflithography.

Under one photon excitation conditions it has been shown that sulfoniumand iodonium salts are effective for the generation of Brønsted acids.Methods for the synthesis of sulfonium salts are well documented in J.L. Dektar and N. P. Hacker, “Photochemistry of Triarylsulfonium Salts”,J. Am. Chem. Soc. 112, (1990) 6004-6015 which are incorporated herein byreference. Additional methods for synthesizing onium salts of the thegeneral type described in the invention can be prepared convenientlyfrom aryl aliphatic sulfides and primary aliphatic halides or benzylhalides, by well known methods such as those described in Lowe, P. A.,“Synthesis of Sulfonium Salts”, The Chemistry of the Sulfonium Group(Part 1), ed. C. J. M. Sterling, John Wiley & Sons, Ltd., (1981), p 267et seq and as described in U.S. Pat. Nos. 5,302,757, 5,274,148,5,446,172, 5,012,001, 4,882,201, 5,591011, and 2,807,648, which are allincorporated herein by reference. Methods for the synthesis of iodoniumsalts are well documented in C. Herzig and S. Scheiding, DE 4,142,327,CA 119,250,162 and C. Herzig, EP 4,219,376, CA 120,298,975 and U.S. Pat.Nos. 5,079,378, 4,992,571, 4,450,360, 4,399,071, 4,310,469, 4,151,175,3,981,897, and 5,144,051 which are incorporated herein by reference.

It is known to those skilled in the art that epoxide-containing monomersexhibit relatively small shrinkage upon polymerization. It is also knownthat expoxide monomers as well as others, such as vinyl ether monomers,can be photo-polymerized under one photon excitation conditions usingiodonium salts and sulfonium salts as photoacid generating initiators asdescribed by: Crivello, J. V.; Lam, J. H. W. Macromolecules, 1977, 10,1307; DeVoe, R. J.; Sahyn, M. R. V.; Schmidt, E. Can. J. Chem. 1988, 66,319; Crivello, J. V.; Lee, J. J. Polym. Sci. Polym. Chem. Ed. 1989, 273951; Dektar, J.; Hacker, N. P. J. Am. Chem. Soc. 1990, 112, 6004;Crivello, J. V.; Lam, J. H. W.; Volante, C. N. J. Rad. Curing, 1977, 4,2; Pappas, S. P.; Pappas, B. C.; Gatechair, L. R.; Jilek, J. H. Polym.Photochem. 1984, 5, 1; Welsh, K. M.; Dektar, J. L.; Garcia-Garibay, M.A.; Hacker, N. P.; Turro, N. J. J. Org. Chem. 1992, 57, 4179; Crivello,J. V.; Kong, S. Macromolecules, 2000, 33, 825, which are incorporatedherein by reference.

It is known that dialkyl aryl sulfonium ions—as described by Saeva, F.D.; Morgan, B. P. J. Am. Chem. Soc., 1984, 106, 4121; Saeva, F. D.Advances in Electron Transfer Chem. 1994, 4, 1, which are incorporatedherein by reference—and iodonium salts can be sensitized throughelectron transfer by the addition of other molecules. These includeClass I and Class II photoacid generating species, as described by Saevaet al. (cited above).

SUMMARY OF THE INVENTION

One object of the invention is to provide compounds and compositionswhich can be efficiently photoactivated by two- or multi-photonexcitation to yield acid and/or radical species and which consequentlyovercome the limitations associated with conventional compounds andcompositions.

This and other objects have been achieved by the present invention, thefirst embodiment of which provides a compound or composition, whichincludes:

-   -   at least one chromophore having a simultaneous two-photon or        multi-photon absorptivity;    -   at least one photoacid or radical generator in close proximity        to the chromophore;    -   wherein the generator may be a sulfonium, selenonium, or        iodonium group, or other acid- or radical generating group. The        present invention is not restricted to acid-generators        consisting of only sulfonium, selenonium or iodonium groups.

Another embodiment of the present invention provides a method for makingan article, which includes contacting the above compound or compositionwith at least one polymerizable or cross-linkable monomer, oligomer, orprepolymer, or acid-modifiable medium (such as ester-functionalizedchemically amplified resins);

-   -   irradiating the compound or composition to cause a simultaneous        two-photon or multiphoton absorption in the chomophore; and    -   polymerizing the monomer, oligomer, or prepolymer, or affecting        a chemical change in an acid-modifiable medium. The invention        can be used for the fabrication of articles by scanning of a        focused laser beam or by multiple-beam interference.

Another embodiment of the present invention provides an article,produced by the above process.

Another embodiment of the present invention provides a method forgenerating a Brønsted or Lewis acid and/or radical, which includesirradiating the above compound or composition to cause a simultaneoustwo-photon or multiphoton absorption in the chomophore.

Another embodiment of the present invention provides a compound orcomposition, which includes:

-   -   a first means for simultaneously absorbing two or more photons;    -   a second means for producing an electronically excited state        upon simultaneous absorption of two or more photons;    -   a third means for generating a Brønsted or Lewis acid and/or        radical upon reaction with the excited state;    -   wherein the third means includes at least one sulfonium,        selenonium, or iodonium group, or other acid- or radical        generating group.

Another embodiment of the present invention provides an apparatus, whichincludes:

-   -   a compound or composition, which includes:        -   a first means for simultaneously absorbing two or more            photons;        -   a second means for producing an electronically excited state            upon simultaneous absorption of two or more photons;        -   a third means for generating a Brønsted or Lewis acid and/or            radical upon reaction with the excited state;    -   wherein the third means includes at least one sulfonium,        selenonium, or iodonium group, or other acid- or radical        generating group; and    -   a means for irradiating the compound or composition.

BRIEF DESCRIPTION OF THE FIGURES

A more complete appreciation of the invention and many of the attendantadvantages thereof will be readily obtained as the same becomes betterunderstood by reference to the following detailed description whenconisidered in connection with the accompanying drawings.

FIG. 1. Two-photon dye covalently attached to a photoacid.

FIG. 2. Two-photon dye non-covalently attached to a photoacid.

FIG. 3. Photopolymerization kinetics of cyclohexene oxide initiated bydifferent triphenylamine sulfonium salts in dichloromethane irradiatedat 300 nm. Concentration of monomer: 7.91 mol/L; concentration ofinitiator: 3.16×10⁻³ mol/L. Lines are a guide to the eye.

FIG. 4. Photopolymerization initiated by different initiators in CH₂Cl₂at 419 nm [monomer]: 7.906 mol/L; [initiator]: 7.906×10⁻³ mol/L.

FIG. 5. Conversion of epoxy acrylate CN-115 initiated by 87 monitored byIR at 810 cm⁻¹. Resin: MeCN, 20% w.t. of CN115; 87, 2% w.t. of CN115.

FIG. 6 a Conversion of epoxy acrylate CN-115 initiated by differentpiperazine stilbene systems monitored by IR Solvent: Tetrahydrofuran 20%w.t. of CN115.

FIG. 6 b. Conversion of epoxy acrylate CN-115 initiated by differentpiperazine bistyrylbenzene systems monitored by IR Solvent:Tetrahydrofuran 20% w.t. of CN115.

FIG. 7. TPE (▪) and relative acid-yield efficiency spectrum (∘) of 41 inacetonitrile (4.0×10⁻⁴ M). δis given in units of GM=1×10⁻⁵⁰ cm⁴ sphoton⁻¹. The inset is a plot of log [H⁺] against log [excitationpower/mW] at 745 nm. The smooth curve is the best fit of a line to thedata and has a slope of 2.3.

FIG. 8. Structures of some conventional PAGs.CD1012=[4-[(2-hydroxytetradecyl)oxy]phenyl]phenyliodoniumhexafluoroantimonate (Sartomer), ITX=isopropylthioxanthone, DPI-DMASdiphenyliodonium 9,10-dimethoxyanthracenesulfonate, TPStriphenylsulfonium hexafluoroantimonate.

FIG. 9. Images of microstructures created by patterned two-photonirradiation of an epoxide resin containing the compound 41. (a).Scanning electron micrograph (SEM) of microstructures created withaverage exposure powers of 1-5 mW. (b). Optical transmission micrographof a “stack-of-logs” photonic bandgap structure fabricated with anaverage power of 3.5 mW. (c). SEM of the microstructure shown in (b).

FIG. 10. Scanning electron micrograph of free-standing columnar featuresformed by two-photon-induced polymerization of a liquid epoxide resincontaining 41.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Various other objects, features and attendant advantages of the presentinvention will be more fully appreciated as the same becomes betterunderstood from the following detailed description of the preferredembodiments of the invention.

Here we teach that compounds preferably derived from TPA dyes, such asD-α-D, D-A-D and A-D-A as described above, but in which the dye skeletonis finctionalized with a group capable of generating a Lewis or BrønstedAcid and/or radical after excitation of the dye moiety, can generatereactive species, and preferably acids or radical species. Inparticular, dyes containing either a sulfonium group or an iodoniumgroup in a single molecule can be effective at generating Lewis orBrønsted Acids (and/or radicals) under one, two, or higher order photonexcitation. These acids or radicals can subsequently react withadditional species in a beneficial manner. For example, these materialscan be used beneficially as one or two-photon initiators forpolymerization of expoxide containing monomers. These compounds exhibitenhanced two-photon or multi-photon absorptivities and allow one tocontrol the position of two-photon or multi-photon absorption bands.

To ensure a more complete understanding of the invention, the followingdefinitions are preferred:

By the term “bridge”, it is meant a molecular fragment that connects twoor more chemical groups.

By the term “donor”, it is meant an atom or group of atoms with a lowionization potential that can be bonded to a π-conjugated bridge.Exemplary donors, in order of increasing strength, are (where R denotesan alkyl, aryl, or alkoxy group as defined below, where X(O) indicatesthat the element oxygen is double bonded to the element X, and where *indicates the point of attachment to the π-conjugated bridge):

-   -   I<Br<Cl<F<OC(O)R<SH<OH<SR<OR<NHC(O)R<NH₂<NHR<NR₂<S⁻<O⁻.

Other donors that have donating strength greater than SR include:

By the term “acceptor”, it is meant an atom or group of atoms with ahigh electron affinity that can be bonded to a π-conjugated bridge.Exemplary acceptors, in order of increasing strength, are (where Rdenotes an alkyl, aryl, or alkoxy group as defined below, where X(O)indicates that the element oxygen is double bonded to the element X, andwhere * indicates the point of attachment to the π-conjugated bridge):

-   -   C(O)NR₂<C(O)NHR<C(O)NH₂<C(O)OR<C(O)OH<C(O)R<C(O)H<CN<S(O₂)R<NO₂.

Other acceptors that have accepting strength greater than C(O)R include(where R denotes an alkyl, aryl, or alkoxy group as defined below):

A more complete discussion of what is meant by electron donors ordonating groups and electron acceptors or electron accepting groups maybe found in J. March, Advanced Organic Chemistry: Reactions, Mechanismsand Structure, Fourth edition, Wiley-Interscience, New York, 1992,Chapter 9, which is incorporated herein by reference.

By the phrase “aromatic group”, it is meant a carbocyclic group thatcontains 4n+2 π-electrons where n is an integer (and which maypreferably have values of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,15, 16, 17, 18, 19, 20, 21, 22, 23, and 24). Exemplary aryl groupsinclude phenyl, naphthyl anthracenyl, and pyrenyl.

By the phrase “heteroaromatic group”, it is meant a cyclic group ofatoms, with at least one atom within the ring being an element otherthan carbon, that contains 4n+2 π-electrons where n is an integer (andwhich may preferably have values of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, and 24). Exemplaryheteroaromatic groups include furanyl, thiophenyl, pyrrolyl,selenophenyl and tellurophenyl. A more complete discussion ofaromaticity and heteroaromaticity can be found in J. March, AdvancedOrganic Chemistry: Reactions, Mechanisms and Structure, Fourth edition,Wiley-Interscience, New York, 1992, Chapter 2, which is incorporatedherein by reference.

By the term “chromophore”, it is meant a molecule or aggregate ofmolecules that can absorb electromagnetic radiation.

By the term “simultaneous”, it is meant that two events that occurwithin the period of 10⁻¹⁴ sec or less.

By the phrase “excited state”, it is meant an electronic state of amolecule wherein electrons populate an energy state that is higher thananother energy state for the molecule.

By the phrase “two-photon absorption”, it is meant the process wherein amolecule is promoted to an excited state by the simultaneous absorptionof two quanta of electromagnetic radiation.

By the phrase “multi-photon absorption”, it is meant a process wherein amolecule absorbs is promoted to an excited state by the simultaneousabsorption of two or more quanta of electromagnetic radiation.

A “π-conjugated bridge” contains covalent bonds between atoms that bothhave σ-(sigma) and π-bonds formed between two atoms by overlap of theiratomic orbitals (s+p hybrid atomic orbitals for σ bonds; p atomicorbitals for r bonds) with two orbitals (sp³, sp², sp) overlappingend-to-end to form a a bond lying directly between the nuclei.

In particular, when two p orbitals are standing perpendicular to theσ-bonded skeleton and overlapping sideways, a π-bond is formed. Whenthere are adjacent p orbitals on each side of an atom, and they overlapwith the p orbital on that atom, a situation is created such that a moreextended π-orbital is formed in which the electrons in the orbital areno longer confined between two atoms, but rather are delocalized over agreater number of nuclei. For this to occur, each successive atombearing a p orbital for overlap must be adjacent to the last. (Sidewaysoverlap of p orbitals is not significant for atoms more than a bondlength apart, that is, ˜1.5 Å.)

This delocalization of π-electrons is of central importance to thechemical and physical properties of unsaturated molecules. Inparticular, a π-conjugated bridge is one having a formal structure thatcontains double or triple bonds alternating with single bonds where thedouble and triple bonds are capable of further π overlap with eachother. Such bridges are said to be π-conjugated and include conjugateddouble or triple bonds.

By the phrase, “heterolytic cleavage”, it is meant the fragmentation ofa two-electron chemical bond such that the two electrons that composedthe bond both reside on one of the two fragments formed.

A more complete discussion of aromaticity and heteroaromaticity can befound in J. March, Advanced Organic Chemistry. Reactions, Mechanisms andStructure, Fourth edition, Wiley-Interscience, New York, 1992. page 205.

By the phrase, “homolytic cleavage”, it is meant the fragmentation of atwo-electron chemical bond such that each of the two fragments formed isformed with one of the two electrons that composed the bond.

A Brønsted acid is a proton or a proton donor.

A Lewis acid is a species that is electron deficient and behaves as anelectron acceptor.

A resin is a mixture of materials and/or compounds at least one of whichis capable of undergoing a chemical reaction that can change thephysical properties of the mixture. For example, it can render themixture less soluble or more soluble in a solvent.

A radical is a species that possesses one or more unpaired electrons.

A binder is a material and/or compound, which is a component of a resin,and which can increase the viscosity of the resin to such a point thatthe resin can be conveniently cast into a film under suitable processingconditions.

Photochemical hardening is a process in which the viscosity ofsolubility of a material increases upon exposure to electro-magneticradiation, preferably from wavelengths of 100 nm to 1600 nm.

A negative resist is a resin whose solublity, in a given solvent,decreases upon exposure to electromagnetic radiation, preferably fromwavelengths of 100 nm to 1600 nm.

A positve resist is a resin whose solublity, in a given solvent,increases upon exposure to electromagnetic radiation, preferably fromwavelengths of 100 nm to 1600 nm.

By the phrase, “photochemically effective amounts”, it is meant that thecomponents of the photoinitiator system are present in amountssufficient for the resin to undergo photochemical hardening uponexposure to light of the desired wavelength.

By radical generator it is meant a species that generates a radicalfollowing an activation process. Such activation processes can include,but are not limited to the following: heating; direct photoexcitation ofthe radical generator; indirect activation of the radical generator byenergy transfer from another photoexcited species; transfer of anelectron to or from the radical generator.

By photo-activated radical generator it is meant a group that uponexposure to electromagnetic radiation generates a radical. Examples ofphoto-activated radical generators include, but are not limited to thefollowing species: Some examples of radical generators include:arylborate anions in the presence of a photosensitizer; benzoin;benzophenone; sulfonium ions; iodonium ions; acylphosphine oxides.Further examples of photo-activated radical generators can be found in:R. S. Davidson, J. Photochem. Photobiol. A: Chem. vol. 73 (1993) pp.81-96; U.S. Pat. Nos. 6,335,144, 6,316,519, 6,296,986, 6,294,698,6,287,749, 6,265,458, 6,277,897, 6,090,236; and patents cited therein,which are incorporated herein be reference.

By an acid generator it is meant a species that generates a Brønsted orLewis acid following an activation process. Such activation processescan include, but are not limited to the following: heating; directphotoexcitation of the acid generator; indirect activation of the acidgenerator by energy transfer from another photoexcited species; transferof an electron to or from the acid generator.

By photoacid generator it is meant a group that upon exposure toelectromagnetic radiation generates a Brønsted or Lewis acid. Examplesof photoacid generators include, but are not limited to the followingspecies: sulfonium, selenonium, and iodinium salts, arene-ironcyclopentadienyl complexes, 4-nitrobenzylsulfonates andperfluorobenzylsulfonates (Shirai, M.; Tsunooka, M. Prog. Polym. Sci.1996, 21, 1); dialkylphenacylsulfonium salts and3,5-dialkyl-4-hydroxyphenyl sulfonium salts (Crivello, J. V.; Lee, J. L.Macromol. 1981, 14, 1141).

The present invention provides for compounds and/or compositions thathave large two-photon or higher-order absorptivities, and which yieldLewis or Brønsted acids (and/or radicals) after multi-photon excitation.It is preferable in the general design scheme of this invention that amulti-photon-excitable chromophore fragment and an acid-generating groupare held in close proximity to one another (at a distance that is lessthan or equal to 20 Å). This can be achieved by connecting thechromophore and the acid generator using a covalent linkage, asillustrated in FIG. 1. However, the invention is not limited tocompositions of matter involving only a covalent linkage of thechromophore and acid generator. Any mechanism that keeps the chromophoreand the acid generator in close proximity is suitable, and thisgeneralized design scheme is illustrated in FIG. 2. The associationmechanisms for the design scheme of FIG. 2 can include, but are notlimited to, ion-pairing effects, hydrogen-bonding, charge-transfercomplex formation, perfluoroaryl-aryl electrostatic interactions,π-stacking associations, coordinative-bond formation, and dipole-dipolepairing.

In compositions wherein the chromophore and the acid generator arecovalently linked, the molecule may be any two-photon dye skeleton, suchas D-π-D, A-π-A, D-A-D or A-D-A, as described in U.S. Pat. No.6,267,913, that is further derivatized with at least one photoacidgenerator or radical generator, such as either a sulfonium or aniodonium group. Moreover, and preferably, the molecules of the inventioncan be described as a two-photon dye skeleton of the form D-π-D, A-π-A,D-A-D or A-D-A, that may have the following substituents:

-   -   i. alkyl: a linear or branched saturated hydrocarbon group with        up to 25 carbons; —(CH₂CH₂O)_(α)—(CH₂)_(β)OR_(a1);        —(CH₂CH₂O)_(α)—(CH₂)_(β)NR_(a2)R_(a3);        —(CH₂CH₂O)_(α)—(CH₂)_(β)CONR_(a2)R_(a3);        —(CH₂CH₂O)_(α)—(CH₂)_(β)CN; —(CH₂CH₂O)_(α)—(CH₂)_(β)Cl;        —(CH₂CH₂O)_(α)—(CH₂)_(β)Br; —(CH₂CH₂O)_(α)—(CH₂)_(β)I; or        —(CH₂CH₂O)_(α)—(CH₂)_(β)-Phenyl, where R_(a1), R_(a2), and        R_(a3) are independently either H or a linear or branched        hydrocarbon group with up to 25 carbons, α is 0-10 and β is 1-25        (which ranges include all values and subranges therebetween,        including 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,        17, 18, 19, 20, 21, 22, 23, 24and 25 as appropriate);    -   ii. alkoxy: OR_(a4), where R_(a4) can be either alkyl, aryl,        sulfonium, iodonium, or monomer as described below;    -   iii. monomer and pre-polymer substituents: such as those which        could contain, but are not limited to vinyl; allyl; 4-styryl;        acrylate; methacrylate; acrylonitrile; dicyclopentadiene;        norbornene; cyclobutene; epoxides (e.g. cyclohexene oxide,        propene epoxide; butene epoxide, vinyl cyclohexene diepoxide);        vinyl ethers; (—CH₂)_(δ)SiCl₃; (—CH₂)_(δ)Si(OCH₂CH₃)₃; or        (—CH₂)_(δ)Si(OCH₃)₃, where δ is 0-25 (which range includes all        values and sub-ranges therebetween, including 0, 1, 2, 3, 4, 5,        6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22,        23, 24, and 25); (further examples of monomer and pre-polymer        functionalities which may be pendant on the two-photon dye        skeleton can be found in U.S. Pat. Nos. 5,463,084, 5,639,413,        6,268,403, 4,689,289, 4,069,056, 4,102,687, 4,069,055,        4,069,056, 4,058,401, 4,058,400, 5,086,192, 4,791,045,        4,090,936, 5,102,772, and 5,047,568, and patents cited therein,        which are incorporated herein by reference); or    -   iv. aryl: up to a 20-membered aromatic or heteroaromatic ring        system (which range includes all values and subranges        therebetween, including 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,        15, 16, 17, 18, 19, and 20 as appropriate), where the rings can        be substituted independently further with H, alkyl, monomer or        pre-polymer substituents as defined above, sulfonium,        selenonium, iodonium, or other acid or radical generating group,        as described below;    -   and the molecules must have at least one of the following:    -   v. sulfonium: —(CH₂)_(γ)—(C₆H₄)_(δ)—SR_(a5)R_(a6), where R_(a5)        and R_(a6) can be independently alkyl, aryl, or monomer or        pre-polymer, and γ=0 to 25, and δ=0 to 5 and the entire group        carries an overall positive charge (these ranges include all        values and subranges therebetween, including 0, 1, 2, 3, 4, 5,        6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22,        23, 24, and 25 as appropriate).    -   vi. selenonium: —(CH₂)_(γ)—(C₆H₄)_(δ)—SeR_(a5)R_(a6), where        R_(a5) and R_(a6) can be independently alkyl, aryl, or monomer        or pre-polymer, and γ=0 to 25, and δ=0 to 5 and the entire group        carries an overall positive charge (these ranges include all        values and subranges therebetween, including 0, 1, 2, 3, 4, 5,        6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22,        23, 24, and 25 as appropriate).    -   vii. iodonium: —(CH₂)_(γ)—(C₆H₄)_(δ)—IR_(a7), where R_(a7) can        be independently alkyl, aryl, or monomer or pre-polymer, and γ=0        to 25, and δ=0 to 5 and the entire group carries an overall        positive charge (these ranges include all values and subranges        therebetween, including 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,        12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, and 25 as        appropriate).    -   viii. one of several other acid- or radical-generating        functionalities as described below. These could include, but are        not limited to, the following examples: oxoniums,        diarylchloroniums, diarylbromoniums, onium bicarbonates,        nitrobenzylcarbonate esters, 4-nitrobenzylsulfonates,        perfluorobenzylsulfonates, dialkylphenacylsulfonium salts,        3,5-dialkyl-4-hydroxyphenyl sulfonium, sulfones, disulfones,        arylphosphates, cyclopentadienyliron arene complexes.

For the onium functionalities of (ii)-(vii), one or more of thesubstituents pendant on the onium center (e.g. O, S, Se, I) may be partof a fused-ring structure, and two or more of the substituents may bejoined through such a fused ring structure. Note that composition ofmatter numbers 84 and 87 (described below), are some preferred examplesof such fused-ring onium photoacid generators.

Since the cationic selenonium, sulfonium or iodonium moieties areessential, the molecules of the invention preferably also have an anionto provide electroneutrality. Preferred examples of anions include: F⁻,Cl⁻, Br⁻, I⁻, CN⁻, SO₄ ²⁻, PO₄ ³⁻, CH₃CO₂ ⁻, CF₃SO₃ ⁻, NO₂ ⁻, NO₃ ⁻, BF₄⁻, PF₆ ⁻, SbF₆ ^(−, AsF) ₆ ⁻, SbCl₄ ⁻, ClO₃ ⁻, ClO₄ ⁻, C(aryl)₄ ⁻ wherearyl is an aryl group containing 25 or fewer carbon atoms (which rangeincludes all values and subranges therebetween, including 3, 4, 5, 6, 7,8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, and 25as appropriate) and can be additionally substituted with one or morealkyl groups, aryl groups or halogens, for example, B(C₆H₅)₄ ⁻, orB(C₆F₅)₄ ⁻. In the preferred embodiment of the invention, the photoacidmolecules will contain anions that are very weak Lewis bases that areeffectively non-coordinating, such as BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻, AsF₆ ⁻,B(aryl)₄ ⁻ or SbCl₄ ⁻. Preferably, the invention molecules may also havea zwitterionic structure, wherein anions (such as B(aryl)₄ ⁻) arecovalently bound to the cationic fragment, giving an overallelectroneutral structure. Combinations of anions are possible.

In a preferred embodiment, the molecules of the invention should havethe structure:

where X═S or Se and n=0, 1, 2, 3, 4, or 5. Ar₁ and Ar₂ can eachindependently be: a 5-membered heteroaromatic ring; a 6-memberedaromatic ring; or a 6-membered heteroaromatic ring. Ar₁ and Ar₂ can eachindependently be substituted with one or more H, alkyl, alkoxy, or aryl,which itself can be further substituted with one or more sulfonium,selenonium, iodonium, other acid- or radical-generating species, ormonomer or pre-polymer functionalities. R₁, R₂, R₃, and R₄ can beindependently alkyl or aryl, which can be further substituted withsulfonium, selenonium, iodonium, other acid- or radical-generatingspecies, or a monomer or pre-polymer functionality. Y is saidcounterion, and is one of the anions defined previously. The overallcharge on the dye portion of the molecule is denoted by z. Integer p isthe charge on the counterion, integers q and Q and are the number ofanions and cations respectively in the empirical formula and are suchthat the quantity zQ=pq, where pq is a positive integer less than 9(which range includes all values and subranges therein, including 1, 2,3, 4, 5, 6, 7, and 8). The following are provided as illustrativeexamples, but are not limiting cases: z=1, Q=1, p=1, q=1, so pq=1; andz=2, Q=1, p=1, q=2, so pq=2.

For this composition and all compositions described hereafter (exceptwhere explicitly stated otherwise), the two or more substituentsconnected to a given aromatic ring may assume any substitution pattern.As an example, for the composition described immediately above, thesubstitution pattern of the fragments R₁R₂X and the vinyl-group aroundAr₁ may be ortho, meta, or para.

In another preferred embodiment, the molecules of the invention shouldhave the structure:

where X═I, and n=0, 1, 2, 3, 4, or 5. Ar₁ and Ar2 can each independentlybe: a 5-membered heteroaromatic ring; a 6-membered aromatic ring; or a6-membered heteroaromatic ring. Ar₁ and Ar₂ can each independently besubstituted with one or more H, alkyl, alkoxy, or aryl groups, whichitself can be further substituted with one or more sulfonium,selenonium, iodonium, other acid- or radical-generating species, ormonomer or pre-polymer functionalities. R₁ and R₂ can be independentlyalkyl or aryl, which can be further substituted with sulfonium,selenonium, iodonium, other acid- or radical-generating species, or amonomer or pre-polymer functionality. Y is said counterion, and is oneof the anions defined previously. The overall charge on the dye portionof the molecule is denoted by z. Integer p is the charge on thecounterion, integers q and Q and are the number of anions and cationsrespectively in the empirical formula and are such that the quantityzQ=pq, where pq is a positive integer less than 9 (which range includesall values and subranges therein, including 1, 2, 3, 4, 5, 6, 7, and 8).The following are provided as illustrative examples, but are notlimiting cases: z=1, Q=1, p=1, q=1, so pq=1; and z=2,Q=1, p=1, q=2,sopq=2.

In another preferred embodiment, the molecules should have the generalstructure:

where X is O, where n=1, 2, 3, 4, or 5. Ar₁ and Ar₂ can eachindependently be: a 5-membered heteroaromatic ring; a 6-memberedaromatic ring; or a 6-membered heteroaromatic ring. Ar₁ and Ar₂ can eachindependently be substituted with one or more H, allcyl, alkoxy, or arylgroups, which itself can be further substituted with one or moresulfonium, selenonium, iodonium, other acid- or radical-generatingspecies, or monomer or pre-polymer functionalities. R₁ and R₂ can beindependently H, alkyl or aryl, which can be further substituted withsulfonium, selenonium, iodonium, other acid- or radical-generatingspecies, or a monomer or pre-polymer functionality. At least one of Ar₁,Ar₂, R₁ or R₂ must be substituted with a sulfonium, selenonium, oriodonium group, or other acid- or radical generating group. Y is saidcounterion, and is one of the anions defined previously. The overallcharge on the dye portion of the molecule is denoted by z. Integer p isthe charge on the counterion, integers q and Q and are the number ofanions and cations respectively in the empirical formula and are suchthat the quantity zQ=pq, where pq is a positive integer less than 9(which range includes all values and subranges therein, including 1, 2,3, 4, 5, 6, 7, and 8). The following are provided as illustrativeexamples, but are not limiting cases: z=1, Q=1, p=1, q=1, so pq=1; andz=2, Q=1, p=1, q=2, so pq=2.

In another preferred embodiment, the molecules should have the generalstructure:

where X is N and n=0, 1, 2, 3, 4, or 5. Ar₁ and Ar₂ can eachindependently be: a 5-membered heteroaromatic ring; a 6-memberedaromatic ring; or a 6-membered heteroaromatic ring. Ar₁ and Ar₂ can eachindependently be substituted with one or more H, alkyl, alkoxy, or arylgroups, which can be further substituted with sulfonium, selenonium,iodonium, other acid- or radical-generating species, or monomer orpre-polymer functionalities. R₁, R₂, R₃, and R₄ can be independently H,alkyl, or aryl, which can be further substituted with sulfonium,selenonium, iodonium, other acid- or radical-generating species, or amonomer or pre-polymer functionality. At least one of Ar₁, Ar₂, R₁, R₂,R₃, or R₄ must be substituted with a sulfonium, selenonium, or iodoniumgroup, or other acid- or radical generating group. Y is said counterion,and is one of the anions defined previously. The overall charge on thedye portion of the molecule is denoted by z. Integer p is the charge onthe counterion, integers q and Q and are the number of anions andcations respectively in the empirical formula and are such that thequantity zQ=pq, where pq is a positive integer less than 9 (which rangeincludes all values and subranges therein, including 1, 2, 3, 4, 5, 6,7, and 8). The following are provided as illustrative examples, but arenot limiting cases: z=1, Q=1, p=1, q=1, so pq=1; and z=2, Q=1, p=1,q=2,so pq=2.

In another preferred embodiment, the molecules should have thestructure:

where X is I, n=0, 1, 2, 3, 4, or 5, and n′=0, 1, 2, 3, 4 or 5. Ar₁ andAr₂ can each independently be: a 5-membered heteroaromatic ring; a6-membered aromatic ring; or a 6-membered heteroaromatic ring. Ar₃ canbe: a 5-membered heteroaromatic ring; a 6-membered aromatic ring; or a6-membered heteroaromatic ring. Ar₁ and Ar₂ can each independently besubstituted with one or more H, alkyl, alkoxy, or aryl groups, which canbe further substituted with sulfonium, selenonium, iodonium, other acid-or radical-generating species, or monomer or pre-polymerfunctionalities. Ar₃ can be substituted with one or more H, acceptor,alkyl, alkoxy, or aryl groups, which can be further substituted withsulfonium, selenonium, iodonium, other acid- or radical-generatingspecies, or monomer or pre-polymer functionalities. R₁ and R₂ can beindependently: alkyl or aryl which can be further substituted withsulfonium, selenonium, iodonium, other acid- or radical-generatingspecies, or monomer or pre-polymer functionalities. Y is saidcounterion, and is one of the anions defined previously. The overallcharge on the dye portion of the molecule is denoted by z. Integer p isthe charge on the counterion, integers q and Q and are the number ofanions and cations respectively in the empirical formula and are suchthat the quantity zQ=pq, where pq is a positive integer less than 9(which range includes all values and subranges therein, including 1, 2,3, 4, 5, 6, 7, and 8). The following are provided as illustrativeexamples, but are not limiting cases: z=1, Q=1, p=1, q=1, so pq=1; andz=2, Q=1, p=1, q=2,so pq=2.

In another preferred embodiment, the molecules should have thestructure:

where X is S or Se, n=0, 1, 2, 3, 4, or 5, and n′=0, 1, 2, 3, 4 or 5.Ar₁ and Ar₂ can each independently be: a 5-membered heteroaromatic ring;a 6-membered aromatic ring; or a 6-membered heteroaromatic ring. Ar₃ canbe: a 5-membered heteroaromatic ring; a 6-membered aromatic ring; or a6-membered heteroaromatic ring. Ar₁ and Ar₂ can be substituted with oneor more: H, alkyl, alkoxy, or aryl, which can be further substitutedwith sulfonium, selenonium, iodonium, other acid- or radical-generatingspecies, or a monomer or pre-polymer functionality. Ar₃ can besubstituted with: one or more H, acceptor, alkyl, alkoxy, or aryl, whichcan be further substituted with sulfonium, selenonium, iodonium, otheracid- or radical-generating species, or a monomer or pre-polymerfunctionality. R₁, R₂, R₃, and R₄ can be independently: alkyl, or aryl,which can be further substituted with sulfonium, selenonium, iodonium,other acid- or radical-generating species, or a monomer or pre-polymerfunctionality. The overall charge on the dye portion of the molecule isdenoted by z. Integer p is the charge on the counterion, integers q andQ and are the number of anions and cations respectively in the empiricalformula and are such that the quantity zQ=pq, where pq is a positiveinteger less than 9 (which range includes all values and subrangestherein, including 1, 2, 3, 4, 5, 6, 7, and 8). The following areprovided as illustrative examples, but are not limiting cases: z=1, Q=1,p=1, q=1, so pq=1; and z=2, Q=1, p=1, q=2, so pq=2.

In another preferred embodiment, the molecules should have thestructure:

where X is O, n=0, 1, 2, 3, 4, or 5, and n′=0, 1, 2, 3, 4 or 5. Ar₁ andAr₂ can each independently be: a 5-membered heteroaromatic ring; a6-membered aromatic ring; or a 6-membered heteroaromatic ring. Ar₃ canbe: a 5-membered heteroaromatic ring; a 6-membered aromatic ring; or a6-membered heteroaromatic ring. Ar₁ and Ar₂ can each independently besubstituted with: one or more H, alkyl, alkoxy, or aryl, which can befurther substituted with sulfonium, selenonium, iodonium, other acid- orradical-generating species, or a monomer or pre-polymer functionality.Ar₃ can be substituted with: one or more H, acceptor, alkyl, alkoxy,aryl, which can be further substituted with sulfonium, selenonium,iodonium, other acid- or radical-generating species, or a monomer orpre-polymer functionality. R₁ and R₂ can be independently: H, alkyl, oraryl, which can be further substituted with sulfonium, selenonium,iodonium, other acid- or radical-generating species, or a monomer orpre-polymer functionality. At least one of Ar₁, Ar₂, Ar₃, R₁, or R₂ mustbe substituted with one or more sulfonium, selenonium, or iodoniumgroups, or other acid- or radical generating groups. Y is saidcounterion, and is one of the anions defined previously. The overallcharge on the dye portion of the molecule is denoted by z. Integer p isthe charge on the counterion, integers q and Q and are the number ofanions and cations respectively in the empirical formula and are suchthat the quantity zQ=pq, where pq is a positive integer less than 9(which range includes all values and subranges therein, including 1, 2,3, 4, 5, 6, 7, and 8). The following are provided as illustrativeexamples, but are not limiting cases: z=1, Q=1, p=1, q 1, so pq=1; andz=2, Q=1, p=1, q=2, so pq=2.

In another preferred embodiment, the molecules should have thestructure:

where X is N, n=0, 1, 2, 3, 4 or 5, n′=0, 1, 2, 3, 4, or 5 and n′″=0, 1,2, 3, 4, or 5. Ar₁ and Ar₂ can each independently be: a 5-memberedheteroaromatic ring; a 6-membered aromatic ring; or a 6-memberedheteroaromatic ring. Ar₃ can be: a 5-membered heteroaromatic ring; a6-membered aromatic ring; or a 6-membered heteroaromatic zing. Ar₁ andAr₂ can each independently be substituted with: one or more H, alkyl,alkoxy, or aryl, which can be further substituted with sulfonium,selenonium, iodonium, other acid- or radical-generating species, or amonomer or pre-polymer functionality. Ar₃ can be substituted with: oneor more H, acceptor, alkyl, alkoxy, or aryl, which can be furthersubstituted with sulfonium, selenonium, iodonium, other acid- orradical-generating species, or a monomer or pre-polymer functionality.R₁, R₂, R₃, and R₄ can be independently: H, alkyl, or aryl, which can befurther substituted with sulfonium, selenonium, iodonium, other acid- orradical-generating species, or a monomer or pre-polymer functionality.At least one of Ar₁, Ar_(2,) Ar₃, R₁, R₂, R₃, or R₄ must be substitutedwith one or more sulfoniumn, selenonium, or iodonium groups, or otheracid- or radical generating groups. Y is said counterion, and is one ofthe anions defined previously. The overall charge on the dye portion ofthe molecule is denoted by z. Integer p is the charge on the counterion,integers q and Q are the number of anions and cations respectively inthe empirical formula and are such that the quantity zQ=pq, where pq isa positive integer less than 9 (which range includes all values andsubranges therein, including 1, 2, 3, 4, 5, 6, 7, and 8). The followingare provided as illustrative examples, but are not limiting cases: z=1,Q=1,p=1, q=1,so pq=1; and z=2, Q=1, p=1, q=2, so pq=2.

In another preferred embodiment, the molecules should have thestructure:

where X is N, n=0, 1, 2, 3, 4, or 5, n′=0, 1, 2, 3, 4 or 5 and n″′=0, 1,2, 3, 4, or 5. Ar₁ and Ar₂ can each independently be: a 5-memberedheteroaromatic ring; a 6-membered aromatic ring; or a 6-memberedheteroaromatic ring. Ar₃ can be: a 5-membered heteroaromatic ring; a6-membered aromatic ring; or a 6-membered heteroaromatic ring. Ar₁ andAr₂ can each independently be substituted with: one or more H, alkyl,alkoxy, or aryl, which can be further substituted with sulfonium,selenonium, iodonium, other acid- or radical-generating species, or amonomer or pre-polymer functionality. Ar₃ can be substituted with: oneor more H, acceptor, alkyl, alkoxy, or aryl, which can be furthersubstituted with sulfonium, selenonium, iodonium, other acid- orradical-generating species, or a monomer or pre-polymer functionality.R₁, R₂, R₃, and R₄ can be independently: H, alkyl, or aryl, which can befurther substituted with sulfonium, selenonium, iodonium, other acid- orradical-generating species, or a monomer or pre-polymer functionality.At least one of Ar₁, Ar_(2,) Ar₃, R₁, R₂, R₃, or R₄ must be substitutedwith one or more sulfonium, selenonium, or iodonium gropus, or otheracid- or radical generating groups. Y is said counterion, and is one ofthe anions defined previously. The overall charge on the dye portion ofthe molecule is denoted by z. Integer p is the charge on the counterion,integers q and Q and are the number of anions and cations respectivelyin the empirical formula and are such that the quantity zQ=pq, where pqis a positive integer less than 9 (which range includes all values andsubranges therein, including 1, 2, 3, 4, 5, 6, 7, and 8). The followingare provided as illustrative examples, but are not limiting cases: z=1,Q=1, p=1, q=1, so pq=1; and z=2, Q=1, p=2 , so pq=2.

In another preferred embodiment, the composition should contain one ormore sensitizers selected from the group of molecules including:

Class 1 Structures: Compounds where the end groups are electron donatinggroups

-   -   where D_(a) is an electron donating group that is any one of N,        O, or S,    -   where m, n, o are integers such that 0≦m≦10, 0≦n≦10, 0≦o≦10        (which ranges independently include all values and subranges        therebetween, including 1, 2, 3, 4, 5, 6, 7, 8, and 9); and        -   where X, Y, Z are independently selected from the group            including: CR_(k)═CR₁; O; S; N—R_(m)        -   where R_(e), R_(f), R_(g), R_(h), R_(i), R_(j), R_(k),            R_(l), R_(m) are defined in NOTE 1.            R_(a), R_(b), R_(c), R_(d)    -   wherein R_(a), R_(b), R_(c), R_(d) are independently selected        from the group including: H; a linear or branched alkyl group        with up to 25 carbons; —(CH₂CH₂O)_(α)—(CH₂)_(β)OR_(a1);        —(CH₂CH₂O)_(α)—(CH₂)_(β)NR_(a2)R_(a3);        —(CH₂CH₂O)_(α)—(CH₂)_(β)CONR_(a2)R_(a3);        —(CH₂CH₂O)_(α)—(CH₂)_(β)CN; —(CH₂CH₂O)_(α)—(CH₂)_(β)Cl;        —(CH₂CH₂O)_(α)—(CH₂)_(β)Br; —(CH₂CH₂O)_(α)—(CH₂)_(β)I;        —(CH₂CH₂O)_(α)—(CH₂)_(β)-Phenyl; various aryl groups; various        fused aromatic rings;    -   where α is 0-10,    -   where β is 1-25,    -   (wherein each of the above ranges independently includes all        values and subranges therebetween, including 1, 2, 3, 4, 5, 6,        7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23        and 24 as appropriate).    -   In the case of Da (Db)=O or S, Rb (Rd)=nothing.        R_(e), R_(f), R_(g), R_(h), R_(i), R_(j), R_(k), R_(l), R_(m)

NOTE 1:

-   -   R_(e), R_(f), R_(g), R_(h), R_(i), R_(j), R_(k), R_(l), R_(m)        are independently selected from the group including H; a linear        or branched alkyl group with up to 25 carbons;    -   —(CH₂CH₂O)_(α)—(CH₂)_(β)OR_(b1);        —(CH₂CH₂O)_(α)—(CH₂)_(β)NR_(b2)R_(b3);    -   —(CH₂CH₂O)_(α)—(CH₂)_(β)CONR_(b2)R_(b3);        —(CH₂CH₂O)_(α)—(CH₂)_(β)CN;    -   —(CH₂CH₂O)_(α)—(CH₂)_(β)Cl; —(CH₂CH₂O)_(α)—(CH₂)_(β)Br;        —(CH₂CH₂O)_(α)—(CH₂)βI;    -   —(CH₂CH₂O)_(α)—(CH₂)_(β)-Phenyl; various aryl; various fused        aromatic rings; NR_(e1)R_(e2);    -   OR_(e3); CHO; CN; NO₂; Br; Cl; I; phenyl;    -   where α is 0-10,    -   where β is 1-25,    -   (wherein each of the above ranges independently includes all        values and subranges therebetween, including 1, 2, 3, 4, 5, 6,        7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23        and 24 as appropriate).

The composition may optionally and preferably contain a second componentthat can be selected from the group including a sulfonium salt suchdescribed in U.S. Pat. Nos. 5,302,757, 5,274,148, 5,446,172, 5,012,001,4,882,201, 5,591,011, or 2,807,648, or an iodonium salt selected fromthe group including those described in C. Herzig and S. Scheiding, DE4,142,327, CA 119,250,162 and C. Herzig, EP 4,219,376, CA 120,298,975and U.S. Pat. Nos. 5,079,378, 4992,571, 4,450,360, 4,399,071, 4,310,469,4,151,175, 3,981,897, 5,144,051, 3,729,313, 3,741,769, 3,808,006,4,250,053 and 4,394,403. Combinations are possible.

It is preferred that the anion for these salts be a nonnucleophilicanion such as BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻, AsF₆ ⁻, or SbCl₄ ⁻.

The two components of the photoinitiator system are preferably presentin photochemically effective amounts, that is, amounts of each componentsufficient to enable the resin to undergo photochemical hardening uponexposure to light of the desired wavelength. Preferably, for every 100parts of monomer, the resin of the invention contains about 0.005 toabout 10 parts (more preferably about 0.1 to about 4 parts) each ofiodonium salt, sensitizer and donor. The amounts of each component areindependently variable and thus need not be equal, with larger amountsgenerally providing faster cure, but shorter shelf life. These rangesinclude all values and subranges therebetween, including 0.007, 0.01,0.05, 0.07, 0.5, 0.7, 0.9, 1, 1.1, 2, 3, 4, 5, 6, 7, 8, 9, and 9.5 partsper 100 parts.

The combination of amine-containing compounds acting as efficientsensitizers for iodonium salts has been reported for one photonexcitation. U.S. Pat. Nos. 4,162,162, 4,268,667, and 4,351,893 and EP127,762 disclose sensitizers containing constrained amino-ketone groupsfor bi-imidazole initiators in addition polymerization. U.S. Pat. No.4,505,793 discloses constrained coumarin sensitizers for triazineinitiators. Amino group-containing-coumarins and constrained coumarinsare also disclosed in U.S. Pat. Nos. 4,278,751, 4,147,552, and 4,366,228and U.K. Patent 2,083,832 for use as triplet sensitizers forcyclo-addition reactions or for use as sensitizers for radicalpolymerization in combination with arylaminoacetic acids. References tothese compounds are also found in Polym. Eng. Sci. 1983, 23, 1022-1024.This article mentions the utility of arninoketocoumarin compounds assensitizers with alkoxypyridinium salts. Photoreactions of coumarincompounds are also mentioned in J. Org. Chem. 1984, 49, 2705-2708. U.S.Pat. No. 4,250,053 teaches constrained coumarin as a sensitizer ofiodonium salt for cationic polymerization. We teach that the abovecombination of two-photon sensitizers shown in Classes 1-I to 1-IV aboveand iodonium or sulfoniums are excitable by two-photon and multi-photonexcitation and should therefore have advantageous properties notavailable for the simple amino-ketone dye, coumarines and relatedcompounds described previously.

Furthermore, U.S. Pat. No. 4,921,827, which is incorporated herein byreference, teaches that constrained alkylamino (particularly julolidino)ketone sensitizers increase the rate of polymerization when used incombination with iodonium salts. Thus we teach that two-photon dyes inwhich R_(a), R_(b), R_(c), R_(d) as described for Class 1-I, Class 1-II,Class 1-III, and Class 1-IV above are preferably part of a constrainedjulolidine ring. The large electron affinity of the iodonium groups,together with the electron-rich nature of the two-photon chromophoresdescribed in Class 1-I, Class 1-II, Class 1-III, and Class 1-IV above,strongly favors formation of a charge-transfer complex between thetwo-photon chromophores and the iodonium cation, which advantageouslykeep the species in close proximity, and which increases the efficiencyof the two-photon and multi-photon induced sensitization process.

The invention, as defined in part by FIG. 1, includes compositions inwhich the multi-photon excitable molecular fragment may be a speciesother than those detailed above. Preferred examples of alternativemulti-photon-excitable molecular fragments include, but are not limitedto the following species: Disperse Red 1 (Delysse, S.; Raimond, P.;Nunzi, J.-M., Chem. Phys. 1997, 219, 341); Coumarin 120, Rhodarnine B(Fischer, A.; Cremer, C.; Stelzer, E. H. K., Appl. Opt. 1995, 34, 1989);AF-50 (Mukheijee, N.; Mukheree, A.; Reinhardt, B. A., Appl. Phys. Lett.1997, 70, 1524); AF-250 (Swiatkiewicz, J.; Prasad, P. N.; Reinhardt, B.A. Opt. Comm. 1998, 157, 135); and 4,4′-dicarbazolyl-stilbene (Segal,J.; Kotler, Z.; Ben-Asuly, S. M. A.; Khodorkovsky, V. Proc. Soc.Photo-Opt. Instrum. Eng. 1999, 3796, 153).

The invention, as defined in part by FIG. 1, includes compositions inwhich the photoacid generator fragment may be a species other than thosedetailed above. Preferable examples of alternative photoacid generatorfragments include, but are not limited to the following species:4-nitrobenzylsulfonates and perfluorobenzylsulfonates (Shirai, M.;Tsunooka, M. Prog. Polym. Sci. 1996, 21, 1); dialkylphenacylsulfoniumsalts and 3,5-dialkyl-4-hydroxyphenyl sulfonium salts (Crivello, J. V.;Lee, J. L. Macromol. 1981, 14, 1141).

The invention as described is not intended to be specific to anyparticularly mechanism of coupling between the two-photonabsorbingchromophore and the photoacid generating fragment. Preferred examples ofpossible coupling mechanisms include electron-transfer, exciplexformation, and energy transfer. One or more mechanisms can occur in theacid-generating photochemistry of a given molecule of the invention, andwhich mechanisms occur will depend upon the nature of thetwo-photon-absorbing chromophore and of the photoacid generatingfragment. By analogy, such mechanisms of coupling can be used togenerate radical species as well, as should be evident to one skilled inthe art.

The compositions of the invention are photoacid generator molecules thatcan be efficiently activated by multi-photon excitation. Thecompositions themselves may exist as crystals, mesoscopic phases,polymers, glasses, liquids or gases. The compositions may be used aloneor in combination with other crystals, mesoscopic phases, polymers,glasses, liquids, or gases.

A particularly convenient and effective form of an optical element inaccordance with the invention involves dispersing the multi-photonabsorbing photoacids in a polymeric or prepolymeric binder. Themulti-photon absorbing photoacids can be mixed into the binder, orincorporated by grafting the chromophore onto the polymer, prepolymer ormonomer constituents. Preferable binders include, for example,polystyrene, polyacrylonitrile, polymethacrylate, poly(methylmethacrylate), poly(vinyl alcohol), copolymers of methyl methacrylateand methacrylic acid, copolymers of styrene and maleic anhydride andhalf ester-acids of the latter, as well as many others. Combinations arepossible.

It is preferred that the polymeric binder be highly transparent so thatthe transparency of the molecules utilized in the practice of thisinvention can be advantageously employed. However, it is a uniquefeature of the invention that even in the case where the binder hasstrong absorption at the wavelength required to initiate single-photonprocesses, the chromophores may still be excited by the two-photon ormulti-photon absorption process.

Generally, the methods according to invention are carried out byconverting a multi-photon absorbing molecule to an electronicallyexcited state by absorption of at least two photons of radiation. Thegeneration of acid following excitation then facilitates numerousapplications. The molecule may be irradiated with visible, ultravioletor infrared radiation. Preferably, the molecule is irradiated atwavelengths from 300 to 1100 nm, which range includes all values andsubranges therebetween, including 400, 500, 600, 700, 800, 900, and 1000nm.

By changing the length and nature of the π-bridge and the strength andnature of the donor and/or acceptor groups, it is possible to controlseveral important molecular photophysical characteristics. Theseinclude, for example, the position and strength of the two-photon (orhigher-order) absorption band(s), the energies of the lowest-occupiedand highest unoccupied molecular orbitals, the excited-state lifetimes,and the fluorescence efficiency. The composition of the π-conjugatedbridge and the donor/acceptor groups can also be modified in such a waythat the ease with which the material dissolves into a variety of hostmedia—including liquids and polymeric hosts—is advantageously varied.

Compositions of the type described above may, in principle, be used forthe photo-activated transformation of any acid-modifiable host medium.Examples of acid-modifiable materials include, but are not limited to:cationically polymerizable and cross-linkable media, catalyzedstep-growth polymerizable and cross-linkable media, acid-cleavableester-functionalized chemically amplified resins (as discussed in U.S.Pat. No. 6,136,500, herein incorporated by reference), polymerizable orcross-linkable materials containing acid-activated polymerizationcatalysts, and acid-sensitive biological media such as polypeptides andproteins. Preferred materials of these types are discussed in U.S. Pat.No. 5,514,728, which is incorporated herein by reference.

One especially preferable class of such materials includes monomers,oligomers, and or cross-linkable materials containing a cationicallypolymerizable group, such as epoxides, cyclic ethers, vinyl ethers,vinylamines, lactones, and cyclic acetals. Materials of this type arediscussed in U.S. Pat. No. 5,514,728, incorporated herein by reference.Combinations are possible.

The molecules of this invention can be used for multi-photon-excitationinitiated ring-opening methathesis polymerization ROMP). It is knownthat certain ROMP catalysts will initiate living ROMP of small-ringcyclic alkenes upon the introduction of acid (Lynn, D. M.; Mohr, B.;Grubbs, R. H.; Henling, L. M.; Day, M. W. J. Am. Chem. Soc. 2000, 122,6601). Multi-photon activatable ROMP can then be achieved by irradiatinga mixture containing a ROMP medium to which has been added the moleculesof this invention.

Onium salts are also well known to generate radicals which can activatefree radical polymerization and cross-linking. As such, the molecules ofthe invention can also be used for the photopolymerization andphoto-crosslinking of free-radical-polymerizable compounds. Compounds ofthis type contain at least one ethylenically unsaturated double bond.Some preferred examples include monomers, oligomers, and cross-linkablepolymers containing acrylate, methacrylate, acrylamide, methacrylamide,and vinyl functionalities. Free-radical-polymerizable compounds aredescribed in U.S. Pat. No. 5,514,728, incorporated herein by reference.In cases where the solubility of the resin in a selected solventdecreases upon exposure to radiation, the resins are termed negativeresists. Preferable examples of negative resist that could be used inaccord with this invention are described in U.S. Pat. Nos. 5,463,084,5,639,413, 6,268,403, 4,689,289, 4,069,056, 4,102,687, 4,069,055,4,069,056, 4,058,401, 4,058,400, 5,086,192, 4,791,045, 4,090,936,5,102,772, and 5,047,568, and patents cited therein—which areincorporated herein by reference. Other resists can undergo chemicaltransformations where the solubility of the resin in a selected solventincreases; these resins are termed postive resists. Postive resists arewell known to those skilled in the art of lithography and may be used inaccord with this invention, and some preferred examples are described inU.S. Pat. Nos. 6,346,363 and 6,232,417 which are incorporated herein byreference. The compositions of the invention can generate both acid andradical species. The tendency of a certain molecule of the invention togenerate radicals versus acid will depend upon the specific molecularstructure and the medium in which the molecule is dispersed. Acidgeneration is favored in cases, among other known to those skilled inthe art, for which the molecules selected from those of the inventionbear groups which upon protonation have pKa's less than or equal to 2.Acid generation is disfavored in cases for which the molecules selectedfrom those of the invention bear groups which upon protonation havepKa's greater than 2.

The compositions of matter described in this invention also provide ameans for the direct fabrication of complex microstructures from ceramicmaterials. U.S. Pat. Nos. 6,117,612, 6,129,540, 5,962,108, 5,939,182,5,814,355, and 5,628,952 and patents cited therein—which areincorporated herein by reference—disclose composite materials whichinclude a photoinitiator, a polymerizable resin, and a ceramic additivepresent at a high fraction of weight-loading. Films of the composite canbe pattern-irradiated by masking or stereolithography to form apatterned polymer matrix containing the ceramic additive. Thepolymerized material is then heated to remove the polymer binder and tosinter the ceramic precursor into a hardened ceramic part. The processdisclosed in U.S. Pat. No. 6,117,612 only pertains to one-photoninitiated polymerization and patterning achieved via multi-step maskingor stereolithography. Given the inherent limitations ofstereolithography, the process disclosed in U.S. Pat. No. 6,117,612 isonly capable of producing macro-scale three-dimensional ceramic partshaving feature sizes larger than 100 μm. By the present invention,two-photon- and multi-photon-processible ceramic/pre-polymer compositescan be formulated, wherein the one-photon initiators of U.S. Pat. No.6,117,612 are replaced by the highly efficient two-photon initiators ofthe present invention. Since the initiators of the present invention cangenerate both radicals and a Brønsted or Lewis acid upon irradiation,the prepolymer may be a free-radical-polymerizable species (acrylate,acrylamide, etc.), as described in U.S. Pat. No. 6,117,612, orcationically polymerizable media (epoxides, vinyl ethers, cycle ethers,etc.), the use of which is not described in U.S. Pat. No. 6,117,612.These new formulations can then be used for the direct two-photon(multiphoton) microfabrication of ceramic parts, wherein the desiredthree-dimensional pattern is generated using the two-photon(multiphoton) microfabrication technique and irradiation geometrydescribed earlier.

The inclusion of moieties of known excited-state reactivity inchromophores with strong two-photon or multi-photon absorption allowsthe invention compounds to have a great variety of novel and usefulapplications including, but not limited to, those described below andabove.

The invention two-photon or multi-photon initiators may be used fortwo-photon (multi-photon) generation of charge carriers, includingprotonic conductivity, for example in photorefractive polymers.

The invention two-photon or multi-photon initiators may be used fortwo-photon or multi-photon initiated polymerization.

The invention two-photon or multi-photon initiators may be used forphotoinduced cleavage of activated ester functionalities (such astert-butoxy, tetrahydropyranyl, etc.).

The invention two-photon or multi-photon initiators may be used toinitate changes in a host medium to write holographic information.

The invention two-photon or multi-photon initiators may be used fortwo-photon or multi-photon optical lithography and three-dimensionaloptical memory.

The invention two-photon or multi-photon initiators may be used formicrofabrication of three-dimensional objects.

The invention two-photon or multi-photon initiators may be used to alterthe pH of an arbitrary medium.

The invention two-photon or multi-photon initiators may be used for invivo or in vitro decaging of biochemical agents for biological,physiological, or medicinal purposes, including drug delivery andphotodynamic therapy.

The invention two-photon or multi-photon initiators may be used formodifying and functionalizing an arbitrary surface, photoresistpatterning and processing, surface inking, and patterning printingplates.

The invention two-photon or multi-photon initiators may be used formodifiing, functionalizing, or texturing the surface or sub-surface of abiological tissue, with the aim, for example, of culturing the growth ofcells, or modifying and engineering tissues.

The invention two-photon or multi-photon initiators may be used tophotoactivate reactions which destablize liposome membranes, which inturn may be used for drug delivery, photodynamic therapy, and decagingof agents in diagnostic assays.

The invention two-photon or multi-photon initiators can be used for thefabrication or articles using single-beam tightly focused (numericalaperture of 0.2 to 1.4) laser exposure.

The invention two-photon or multi-photon initiators can be used for thefabrication of three-dimensional objects having 1, 2, and 3-dimensionalperiodicities using multiple-beam-holographic interference exposure.

The invention two-photon or multi-photon initiators can be used for thefabrication of articles having linear dimensions or feature sizesranging from 10 centimeters to 20 nanometers, depending upon thespecific optical excitation geometry employed.

A photo-pattemable medium containing two or more of the two-photon ormulti-photon initiators can be exposed sequentially or in parallel usingdifferent excitation wavelengths to impress two or morethree-dimensional patterns into the same medium, and thereby produce asingle complex three-dimensional object.

A series of one or more photo-patternable media containing one or moreof the two-photon or multi-photon initiators can be used tophoto-pattern a single complex three-dimensional object comprised of twoor more distinct material systems.

A composite medium, consisting of (a) the compositions of the inventionand (b) a self-assembling or self-organizing material (see below), canbe photo-patterned by two- or multi-photon excitation to generate anarticle having structure, possibly on very different length-scales,defined by (1) the impressed photo-pattern and (2) the structureassociated with the self-assembled units. Examples of self-assembling orself-organizing materials that may be used include, but are not limitedto, the following: metal, semiconductor, and metal oxide nanoparticles;polymer, silica, and metal oxide microspheres; block co-polymers thatspontaneously form ordered structures (e.g. lamellae or micro-domains);liquid crystals and liquid-crystal polymers in various phases; colloidalcrystal arrays; lipid-bilayer systems ordered in various phases (e.g.vesicle, hexagonal, or columnar).

A more extensive listing of applications that would be renderedsubstantially more useful by virtue of the large two-photon ormulti-photon absorptivities of the compounds described herein can befound for example in U.S. Pat. Nos. 4,228,861, 4,238,840, 4,471,470,4,333,165, 4,466,080 and 5,034,613, which are incorporated herein byreference.

The multi-photon activatable materials described in this section can beused for the three-dimensional microfabrication of a wide range ofcomplex devices and systems. Preferred examples includemicro-electromechanical structures, micro-electrooptic systems, opticalwaveguides, photonic circuits, optical component couplers, micro-opticalswitching systems, microfluidic devices (such as disclosed in U.S. Pat.No. 6,136,212, which is incorporated herein by reference), and theconstruction of complex patterns and structures used as templates ormicroscaffolds in further fabrication processes.

Triarylamines are preferred as electron donors for two-photonchromophores for photoacids because i) triarylamine radical cations areknown to be very stable, and thus the driving force and rate for bondhomolysis should be improved greatly by the stability of the radicalcation; ii) protonated triarylamino groups are extremely strong acids(Ph₃N⁺H, pK_(a)=−5) and so the presence of this amine functionalityshould not inhibit reactions such as the ring-opening polymerization ofepoxides; and iii) the conditions used in the preparation of aryldialkyl sulfonium salts are compatible with the triarylamine functionalgroup. Triarylamine sulfonium salts are thus particularly suitable.

The sulfonium group(s) can be attached to various sites ontriphenylamines; for example, in the examples in Scheme 1 the sulfoniumgroup is attached to the meta position of a phenyl ring on the donornitrogen atom. The molecules described in Scheme 1 are highly efficientcationic photoinitiators with quantum yields of photoacid generation of˜0.5, independent of the counter-ion.

The sulfonium group can be attached to a two-photon dye by a covalentbond, as shown for the molecules in Scheme 2. The sulfonium group can beattached to various sites in the molecule, as will be described, but, inthe examples shown in Scheme 2, the sulfonium group is attached to themeta position of a terminal phenyl group. Our experiments have shownthat molecules described in this scheme are effective as initiators forthe photopolymerization of a wide range of epoxides, includingcyclohexene oxide, 4-vinyl-cyclohexene diepoxide, EPON SU-8, andARALDITE CY179MA.

The precursor sulfides for bis(styryl)benzene sulfonium salts (type-I)41 and 42 were synthesized using a phase-transfer Homer-Emmons reactionand Pd-catalyzed C—N coupling reactions (Scheme 3). However, the poorsolubility of bis(arylarninostyryl)benzene in the Pd-catalyzed reactionmixture leads to the low yield of product, only 9.9% when R is methyland 16.2% when R is benzyl, and total yields are 4.4% (R=methyl) and7.2% (R=benzyl). Meanwhile, the formation of unknown side products makespurification difficult. Therefore, an improved route for the preparationsuch type of compounds was developed.

The yields in the alternative route, using Pd-catalyzed reactionsfollowed by the Horner-Emmons reaction (Scheme 4), were quite high;87.5% for methyl and 95.4% for benzyl. The low reactivity of4-bromobenzaldehyde makes the Pd-catalyzed direct arylation of aminesdifficult; thus, a protected 4-bromobenzaldehyde derivative was used inthe arylation. The arylation of the amine with the protected4-bromobenzaldehyde afforded a high yield, and, without furtherseparation, the deprotection was fast and complete in the presence ofacid in TVE solution. The total yields for the preparation the precursorsulfides are 50.5% (R=methyl) and 49.7% (R=benzyl).

The syntheses of other types of bis(styryl)benzene sulfonium salts(type-II) 52 and 53 are shown in Scheme 5, wherein the sulfonium groupis attached to an aryl ring closer to the dye center. The triarylaminecan be made with palladium-catalyzed coupling chemistry, and thenformylated under Vilsmeier conditions. The yields of the precursorsulfides by the Horner-Emmons coupling is high, and the final salts canbe easily obtained.

Two A-π-A bis(styryl)benzene sulfide precursors (59) (Scheme 6) and (64)(Scheme7) with terminal electron-withdrawing sulfonium groups weresynthesized. To increase solubility, long alkyl chains were introducedon the central phenyl ring (59) or linked to sulfur (64). 59 has beenprepared by two different methods: the Wittig reaction and theHomer-Emmons reaction (Scheme 6).

Since D-A-D type chromophores have large two-photon cross sections, andsince the sulfonium group is a relatively strong electron acceptor, fourD-A-D type bis(styryl)benzene molecules with sulfonium on the centralring and electron-donating alkoxy or amino donors on both ends wereprepared. To increase the solubility of these species, long allyl chainswere attached. Introduction of the alkoxy group as the donor shifts themolecules' absorption peaks to shorter wavelength, which could beadvantageous for certain applications.

Three synthetic routes to precursor sulfides for such D-A-D typetwo-photon cationic initiators (mono or bis-sulfonium) were investigated(Scheme 8). Following route 1, attempts to synthesize2-methylthio-α,α′-dibromo-p-xylene from 2-methylthio-p-xylene (64), or2,5-di(methylthio)-α,α′-dibromo-p-xylene from2,5-di(methylthio)-p-xylene (65) failed to yield the desired productsusing either N-bromosuccinimde (NBS) or paraformaldehyde/HBr/acetic asbrominating agents. Following route 3, the preparation of2-methylthio-p-benzenedialdehyde was found to be difficult to optimize.Route 2 was, therefore, employed, and the desired precursors (78, 79, 80and 81) could be prepared as shown in Scheme 9. In an attempt to prepare2,5-dibromo-α,α′-dibromo-p-xylene (67) or 2-bromo-α,α′-dibromo-p-xylene(68) using NBS, the bromine radical can attack both α-carbon and phenylring carbon positions. However, the reactivity of the α-carbon is stillhigher than that of the phenyl ring carbon and, therefore, in order tocontrol the product distribution, NBS was added to the reaction mixturein several portions over a relatively long time period. The mono or bisproducts can be easily purified by recrystallization from methanol. Inthe preparation of sulfides from the corrresponding bromides usingt-butylithium followed by sulfur, the yields for butoxylbis(styryl)benzenes (74, 75) are higher than those triphenylaminebis(styryl)benzene compound (76, 77).

Triphenylsulfonium salts are known as UV sensitive cationic and radicalinitiators; like dialkyl sulfonium salts they can be attached toappropriate chromophore so that they act as photo-initiators via anelectron transfer process. Phenothiazine, the first compound in Scheme10, with N and S atoms in the central of three fused rings, is the basisof one method of attachment of a triphenylsulfonium group to atwo-photon chromophore. The sulfur can be arylated to sulfonium and thesecondary amino group affords a site for the extension of a conjugatedsystem, such as those characteristics of D-π-D two-photon absorbingchromophores. As shown in Scheme 10, the molecules (84, 87) wereprepared by first arylating the amine, using a palladium-catalyzedcoupling reaction, and then arylating the sulfide using an iodoniumsalt. The acid-generation quantum yield for 87 ((Φ_(H) ⁺=0.21) is higherthan that for 84 (Φ_(H) ⁺=0.07). 87 can efficiently initiate bothcationic and radical polymerization as shown in FIG. 5.

A triarylamine-triarylsulfonium (Scheme 11) was also prepared in foursteps. 3-bromophenylphenylsulfide was synthesized according toliterature procedures. It was found that 91 is less active thandialkylsulfonium triphenylamine.

Compounds have also been synthesized in which one of two electron donorsis replaced by a nitrogen of the two-nitrogen-containing piperazinering, and where the other secondary amine of the piperazine is linked tothe active sulfonium group using a nucleophilic substitution reaction(e. g. 100, 106).

Stilbene dye-triphenylsulfonium compound 100 has been prepared in sevensteps. Formylation of N,N-dibutylaniline gave 4-N,N-dibutylaminobenzaldehyde (92) in a yield of 79.9%. Reduction of aldehyde 92 withNaBH₄ gave 4-N,N-dibutylamino benzylalcohol (93) in a yield of 89.4%.The preparation of 4-N,N-dibutylamino benzylchloride from alcohol 93 wasunsuccessful using thionyl chloride (SOCl₂). However, chlorination of 93was successful using concentrated hydrochloric acid, which gave ahydrochloride salt 94 in a yield of 96.1%. Since the neutralN,N-dibutylaminobenzylchloride is unstable and easily transformed to acarbocation (deep blue), the hydrochloride salt 94 was used in next stepwithout further purification. The reaction of 94 with triethylphosphitegave phosphonate 95 in a yield of 90.1%. The BOC-protectedpiperazine-functionalized benzaldehyde, 97, was prepared in two steps.Nucleophilic displacement of fluoride from 4-fluorobenzaldehyde withpiperazine gave 4-piperazinobenzaldehyde, 96, which reacted with BOC togive secondary amine-protected compound, 97. It was found that thisnucleophilic substitution reaction is solvent-dependent; DMF gave noneof the desired product, but DMSO was isolated in 48% over two steps. Thereaction of 95 and 97 under Homer-Emmons conditions gave compound 98 ina yield of 74.2%; deprotection of 98 gave the mono-piperzino dye 99 in ayield of 89.7%. Finally, the nucleophilic substitution reaction of 99with 4-fluorophenyldiphenylsulfonium hexafluorophosphate in DMSO gavethe light-sensitive compound 100 in a yield of 73.6%.

Bistyiylbenzene dye-sulfonium compound 106 was prepared in six steps. Inorder to increase solubility of the compound, n-butyl substituents wereemployed on the nitrogen, along with two methoxy groups on the centralring. 1,4-dimethoxyl benzene reacted with formaldehyde in concentratedhydrochloric acid in the presence of hydrogen chloride gas to give2,5-di(chloromethyl)-1,4-dimethoxyl benzene 101 in a yield of 56.2%. Thereaction of 101 with triethylphosphite gave tetraethyl2,5-bismethoxyl-p-xylene phosphonate (102) in a yield of 94.3%. 102reacted with N,N-di-n-butyl-4-aminobenzaldehyde under Homer-Emmonsconditions to give diethyl4-{(E)-2-[4-(dibutylamino)phenyl}ethenyl}-2,5-dimethoxybenzylphosphonate (103) in a yield of 57.8%; excess 102 and a relatively largeamount of solvent were used in the experiment to decrease thepossibility of reaction on both phosphonates. The Homer-Emmons reactionbetween 103 and 97 gaveN-(4-{(E)-2-{4-[4-(1-tert-butoxycarbonyl)piperazin-1-yl]phenyl}ethenyl)-2,5-dimethoxyphenyl]ethenyl}phenyl)N,N-dibutylamine (104) in a yield of 71.4%. Deprotection of 104 gave4-N,N-{2,5-dimethoxy-4-[(E)-2-(4-piperazin-1-ylphenyl)ethenyl]phenyl}ethenyl)aniline(105) in a yield of 85.7%. Finally, the nucleophilic substitutionreaction of 105 with 4-fluorophenyl diphenylsulfoniumhexafluorophosphate gave the target compound 106 in a yield of 70.4%.

Scheme 14 shows the synthesis of a precursor suitable for conversion toa two-photon dye doubly functionalized with triarylsulfonium groups.

Scheme 15 shows examples of two-photon chromophores containing thejulolidine that have been synthesized and that are potential two-photonsensitizers with diphenyliodonium salts through a charge-transferinteraction.

Scheme 16 summarizes acid quantum-yield data for some of the photoacidsdescribed above.

Cationic Photopolymerization

FIG. 3 shows a comparison of the photopolymerization of cyclohexeneoxide using 5, 7, 8 and 9 as initiators. In accord with previousobservations, large anion-dependent variations in thephotopolymerization rate were observed. Sulfonium salt 5, which has atriflate counterion, does not initiate polymerization, even after onehour of irradiation. In contrast, 8 and 9, having a SbF₆ ⁻ anion,rapidly initiate polymerization, leading to 90% conversion to polymer in130 seconds. 8 and 9 were found to initiate polymerization withextremely short induction times relative to triphenylsulfoniumhexafluoroantimonate (TPS), when irradiated at 300 nm, under otherwiseidentical conditions. This demonstrates that triphenylamine sulfoniumsalts are highly efficient cationic initiators that are sensitive to 300nm radiation.

The photopolymerization of cyclohexene oxide initiated by different dyesulfonium salts was measured. From the % conversion versus time curve(FIG. 4), it can be seen that these three sulfonium salts have a highinitiation ability upon irradiation at 419 nm.

Radical Photopolymerization

A typical formulation of epoxy acrylate CN 115 (Sartomer Company, Inc.),initiator, and tetrahydrofuran (20% by weight of CN115) was used forradical polymerization experiments and the conversion of acrylate wasmonitored using IR spectroscopy at 810 cm⁻¹. Upon irradiation, mono- orbi-molecular systems of dye/sulfonium salt undergo inter- orintra-molecular electron-transfer reactions to produce the active phenylradical species, and the radical cation of the dye. The latter mightfurther undergo a secondary reaction to form colorless photo-products,while the phenyl radical can initiate a radical polymerization ofunsaturated acrylates or resins. FIG. 5 illustrates radicalpolymerization initiated by compound 87. The plots of conversion vs.irradiation time (FIG. 6 a, 6 b) show that both the combination systems99 or 105 with triphenylsulfonium hexafluorophosphate (TPS′), and thesingle molecule systems 100 or 106 are more effective than 99 or 105alone. But single molecule systems 100 and 106 are the most efficientinitiators, and both the polymerization rate (initial slope of a curve)and maximal conversion are higher than for others under the sameconditions. The polymerization rate also decreases with the decrease ofconcentration of initiator 100 or 106, but not dramatically. Incontrast, the concentration of the components of the bimolecular systemhas a dramatic influence on the polymerization, the decrease ofconcentration of 99, 105 or sulfonium (TPS) leads to a significantincrease of the induction time, a decrease of polymerization rate, and adecrease in maximal conversion. Therefore, the single moleculedye-sulfonium linked radical initiators are highly efficient in viscousmedia.

Preferable high peak-power lasers (emission wavelengths, and pulsedurations) suitable for two-photon/multiphoton excitation of photoacid-and radical-generators include:

Continuous-wave (CW) mode-locked ML) titanium:sapphire

-   λ_(em)=690-1050 nm, τ_(p)˜80 fs-80 ps-   λ_(em)=345-525 nm (second harmonic), τ_(p)˜80 fs-80 ps.

Optical parametric oscillator pumped by CW ML Ti:sapphire

-   λ_(em)=500-2000 nm (including second-harmonic), τ_(p)˜80 fs.

Amplified ML Ti:sapphire

-   λ_(em)=750-900 nm, τ_(p)˜80 fs-80 ps-   λ_(em)=375-450 nm (second harmonic), τ_(p)˜80 fs-80 ps-   λ_(em)=250-300 nm (third harmonic), τ_(p)˜80 fs-80 ps-   λ_(em)=188-225 nm (fourth harmonic), τ_(p)˜80 fs-80 ps.

Optical parametric amplifier (OPA) pumped by amplified ML Ti:sapphire

-   λ_(em)=300-10,000 nm (including harmonics), τ_(p)˜80 fs-1 ps.

Q-switched Nd:yttrium aluminum garnet (Nd:YAG)

-   λ_(em)=1064 nm, τ_(p)˜5 ns-   λ_(em)=532 nm (second harmonic), τ_(p)˜5 ns-   λ_(em)=355 nm (third harmonic), τ_(p)˜5 ns-   λ_(em)=266 nm (fourth harmonic), τ_(p)˜5 ns.

Q-switched Nd:yttrium vanadate (Nd:YVO₄)

-   λ_(em)=1064 nm, τ_(p)˜5 ns-   λ_(em)=532 nm (second harmonic), τ_(p)˜5 ns-   λ_(em)=355 nm (third harmonic), τ_(p)˜5 ns-   λ_(em)=266 nm (fourth harmonic), τ_(p)˜5 ns.

Q-switched Nd:yttrium lanthanum fluoride (Nd:YLF₄)

-   λ_(em)=1054 nm, τ_(p)˜5 ns-   λ_(em)=527 nm (second harmonic), τ_(p)˜5 ns-   λ_(em)=351 nm (third harmonic), τ_(p)˜5 ns-   λ_(em)=264 nm (fourth harmonic), τ_(p)˜5 ns.

Mode-locked Q-switched Nd:glass

-   λ_(em)=1060 nm, τ_(p)˜5-50 ps-   λ_(em)=527 nm (second hanmonic), τ_(p)˜5 ns -50 ps-   λ_(em)=351 nm (third harmonic), τ_(p)˜5 ns -50 ps-   λ_(em)=264 nm (fourth harmonic), τ_(p)˜5 ns -50 ps.

Dye lasers

-   λ_(em)˜225-940 nm (including harmonics)-   τ_(p)˜500 ps-5 ns, (<5 fs in special cases).

Ruby

-   λ_(em)=694 nm, τ_(p)˜5 ns-   λ_(em)=347 nm (second harmonic), τ_(p)˜5 ns.

Alexandrite

-   λ_(em)=378 nm (second harmonic), τ_(p)˜5 ns.

Picosecond diode lasers

-   λ_(em)=635-1060 nm, τ_(p)˜70-150 ps.

Erbium-doped fiber lasers

-   λ_(em)=1550 nm, 775 nm (second harmonic), τ_(p)=100 fs.

The two-photon absorption cross-sections, δ, are measured by thetwo-photon induced fluorescence method (Xu, C.; Webb, W. W. J. Opt. Soc.Am. B, 1996,13, 481-491) using both femtosecond and nanosecond pulsedlasers as excitation sources. The reference standards used in themeasurement of δ are (1,4-bis(2-methylstyrl)benzene in cyclohexane,rhodamine B in methanol, fluorescein in pH 11 water, and coumarin 307 inmethanol), for which the two-photon properties have been wellcharacterized in the literature (Xu, C.; Webb, W. W., J. Opt. Soc. Am.B, 1996, 13, 481-491; Kennedy, S. M.; Lytle, F. E. Anal Chem., 1986, 58,2643-2647). The δ for a given compound is obtained from experimentallydetermined parameters using:$\delta_{s} = {\frac{S_{s}\eta_{r}\Phi_{r}C_{r}}{S_{r}\eta_{s}\Phi_{s}C_{s}}\delta_{r}}$where S is the detected two-photon induced fluorescence signal, η is thefluorescence quantum yield, and C is the concentration of thechromophore. Φ is the collection efficiency of the experimental setupand accounts for the wavelength dependence of the detectors and opticsas well as the difference in refractive indexes between the solvents inwhich the reference (r) and sample (s) compounds are dissolved. Themeasurements are conducted in a regime where the fluorescence signalshows a quadratic dependence on the intensity of the excitation beam, asexpected for two-photon induced emission.

The nanosecond-pulse measurements are performed using an experimentalset-up described previously (Rumi, M; Ehrlich, J. E; Heikal, A. A.;Perry, J. W.; Barlow, S.; Hu, Z.; McCord-Maughon, D.; Parker, T. C.;Röckel, H.; Thayumanavan, S.; Marder, S. R.; Beljonne, D.; and Brédas,J.-L. J. Am. Chem. Soc., 2000, 122, 9500-9510). The excitation source isa Nd:YAG-pumped optical parametric oscillator (Quanta-Ray, MOPO 730)with a 5-ns pulse duration and 10 Hz repetition rate, tunable over thewavelength range of 430-700 and 730-2000 nm. A two-arm set-up is used tocorrect for fluctuations in the laser intensity. The beam isapproximately collimated over the 1-cm pathlength of the glass cuvette.The concentrations of the solutions are ˜10⁻⁴ M for both the sample andreference compounds. In each arm, the two-photon-induced fluorescence iscollected at right angles to the excitation beam and focused onto aphotomultiplier tube (PMT). Short wave pass filters are used to blockscattered light. The signals are averaged over about 300 pulses.

The femtosecond-pulse measurements are performed using a Ti:Sapphirelaser (Spectra-Physics, Tsunami) as the excitation source. This lasergenerates ˜100 fs pulses at a repetition rate of 82 MHz in thewavelength range of 710-1000 nm. A one-arm set-up is utilized in thisexperiment, and the sample and reference measurements are taken inseries for each excitation wavelength. The beam is focused into a 1-cmpathlength cell containing solutions at concentrations of 10⁻⁴ M-10⁻⁶ M.Fluorescence is detected at 90° with respect to the excitation beam by aPMT after a series of short-wave-pass filters and a monochromator toblock out scattered light. The fluorescence collection is performed atthe same detection wavelength for reference and sample compounds. ThePMT is operated in a single photon counting regime and its output isamplified and read by a frequency counter. The output signal is averagedfor 30 seconds and recorded.

The magnitude of the two-photon absorptivity of a generic medium can becharacterized by the two-photon absorption coefficient, β (having unitsof, e.g., cm/W). β is a macroscopic property of a given material thatdepends upon the specific composition. For the case of a materialcomprised in part or entirely of molecules, the macroscopic two-photonabsorptivity can be related to the molecular two-photon absorptioncross-section, δ, by β=δC/hv, where C is the number density of themolecules in the material (in units of molecules/cm³), h is the Planckconstant, and v is the frequency of the radiation used to two-photonexcite the medium (in units of s⁻¹). β can be measured using severaltechniques, including nonlinear transmission and “Z-scan”, as describedin R. L. Sutherland's Handbook of Nonlinear Optics (New York, MarcelDekker, 1996). At a two-photon excitation wavelength of 800 nm, typicalphotopolymer compositions comprised of conventional photoinitiators willhave two-photon absoiptivities in the range of β=0 to 1.6×10⁻¹¹ cm/W,and more typically, β<1.6×10⁻¹² cm/W .

Several preferred embodiments are given below in paragraphs A-I.

A. A composition of matter which includes a sulfonium, selenonium,iodonium salt, or other acid- or radical generator containing:

-   -   a two-photon absorbing chromophore with a two-photon        cross-section >50×10⁻⁵⁰ cm⁴ s/photon wherein the excited state        of the chromophore can activate the acid/radical generator        towards undergoing a molecular rearrangement generating a        Brønsted or Lewis acid and/or radical;    -   a group or bond that links the chromophore to the acid/radical        generator, bringing the chromophore and the acid/radical        generator into close spatial proximity; and    -   an anion(s).

B. A composition of matter which includes a sulfonium, selenonium, oriodonium salt, or other acid- or radical generator containing:

-   -   a two-photon absorbing chromophore with a two-photon        cross-section >50×10⁻⁵⁰ cm⁴ s/photon, wherein the excited state        of the chromophore can activate the acid/radical generator        towards undergoing a molecular rearrangement generating a        Brønsted or Lewis acid and/or radical;    -   an electrostatic interaction between the chromophore and the        acid/radical generator, the attractive energy associated with        which is greater than 3 kcal/mol, and which keeps both moeities        in close spatial proximity on average, when both compounds are        present in the concentrations of 0.001 M-2M; and    -   an anion(s).

C. A composition of matter which includes a sulfonium, selenonium, oriodonium salt, or other acid- or radical generator containing:

-   -   a two-photon absorbing chromophore with a two-photon        cross-section >50×10⁻⁵⁰ cm⁴ s/photon wherein the excited state        of the chromophore can activate the acid/radical generator        towards undergoing a molecular rearrangement generating a        Brønsted or Lewis acid and/or radical;    -   an electrostatic interaction between the chromophore and the        acid/radical generator, the attractive energy associated with        which is greater than 3 kcal/mol, and which keeps both compounds        in close spatial proximity on average, when both compounds are        present in the concentrations of 0.001 M -2M;    -   wherein the chromophore itself is an anion.

D. A composition according to embodiment A above, in which a two-photonabsorbing chromophore with a two-photon cross-section >50×10⁻⁵⁰ cm⁴s/photon, wherein the excited state of the chromophore can activate theradical/acid generator towards undergoing a molecular rearrangementgenerating a Brønsted or Lewis acid and/or radical, and the chromophoreis a molecule in which two donors are connected to a conjugatedπ-electron bridge (abbreviated “D-π-D” motif).

E. A composition according to embodiment A above, in which a two-photonabsorbing chromophore with a two-photon cross-section >50×10⁻⁵⁰ cm⁴s/photon, wherein the excited state of the chromophore can activate theradical/acid generator towards undergoing a molecular rearrangementgenerating a Brønsted or Lewis acid and/or radical, and the chromophoreis a molecule in which two donors are connected to a conjugatedπ-electron bridge which is substituted with one or more electronaccepting groups (abbreviated “D-A-D” motif).

F. A composition according to embodiment A above, in which a two-photonabsorbing chromophore with a two-photon cross-section >50×10⁻⁵⁰ cm⁴s/photon, wherein the excited state of the chromophore can activate theradical/acid generator towards towards undergoing a molecularrearrangement generating a Brønsted or Lewis acid and/or radical, andthe chromophore is a molecule in which two acceptors are connected to aconjugated π-electron bridge (abbreviated A-π-A” motif).

G. A composition according to embodiment A above in which a two-photonabsorbing chromophore with a two-photon cross-section >50×10⁻⁵⁰ cm⁴s/photon, wherein the excited state of the chromophore can activate theradical/acid generator towards undergoing a molecular rearrangementgenerating a Brønsted or Lewis acid and/or radical, and the chromophoreis a molecule in which two acceptors are connected to a conjugatedπ-electron bridge which is substituted with one or more electrondonating groups (abbreviated “A-D-A” motif).

H. A method of generating a Brønsted or Lewis acid or radical, whichincludes a step of exposing a compound that includes a sulfonium,selenonium, or iodonium salt, or other acid- or radical generator; achromophore having the formula D₁-π-D₂ wherein D₁ and D₂ are electrondonor groups; and 7 includes a bridge of π-conjugated bonds connectingD₁ and D₂; and a group which links the chromophore to the radical/acidgenerator, bringing the chromophore and the radical/acid generator intoclose spatial proximity; and an anion;to pulsed laser radiation andconverting the compound to a multi-photon electronically excited stateupon simultaneous absorption of at least two photons of the radiation bythe compound, wherein the sum of the energies of all of the absorbedphotons is greater than or equal to the transition energy from a groundstate of the compound to the multi-photon excited state, and wherein theenergy of each absorbed photon is less than the transition energybetween the ground state and the lowest single-photon excited state ofthe compound and is less than the transition energy between themulti-photon excited state and the ground state, and the excited stateis capable of transforming the salt through a sequence of one or morereactions to a Brønsted or Lewis acid and/or radical.

I. A method of generating a Brønsted or Lewis acid and/or radical, whichincludes:

-   -   i. exposing a compound, which includes a sulfonium, selenonium,        or iodonium salt, or other acid- or radical generator; a        chromophore and a group or bond which links the chromophore to        the acid/radical generator, bringing the chromophore and the        acid/radical generator into close spatial proximity; and an        anion(s);    -   to pulsed laser radiation;    -   ii. converting the compound to a multi-photon electronically        excited state upon simultaneous absorption of at least two        photons of the radiation by the compound, wherein the sum of the        energies of all of the absorbed photons is greater than or equal        to the transition energy from a ground state of the compound to        the multi-photon excited state and wherein the energy of each        absorbed photon is less than the transition energy between the        ground state and the lowest single-photon excited state of the        compound and is less than the transition energy between the        multi-photon excited state and the ground state; and;    -   iii. generating a Brønsted or Lewis acid and/or a radical from        the excited compound through a sequence of one or more        reactions.

EXAMPLES

Having generally described this invention, a further understanding canbe obtained by reference to certain specific examples, which areprovided herein for purposes of illustration only and are not intendedto be limiting unless otherwise specified.

Example 1

Preparation of 3-bromothioanisole (1). 3-bromobenzenethiol (5 g, 26.44mmol) was added to a solution of sodium methoxide (1.43 g, 26.48 mmol)in 20 ml of anhydrous methanol. The mixture was stirred for 30 min undernitrogen at room temperature and a solution of methyl iodide (4.51 g,31.77 mmol) in 20 ml anhydrous methanol was then added. The reactionmixture was stirred overnight at room temperature, poured into 2 Maqueous NaOH solution (30 ml) and extracted three times with ether (60ml×3). The combined organic layer was washed with saturated sodiumchloride solution and dried over anhydrous magnesium sulfate. Afterremoval of solvent, the product was purified by distillation at 80° C.(0.3 mmHg) and isolated in 86.1% (4.62 g) yield. ¹H NMR(CDCl₃, 500 MHz)δ ppm: 2.44 (s, 3H, CH₃), 7.1-7.4(m, 4H, Ar—H)GC-MS(relative intensity%): 202, 204(1:1, 100, M⁺), 187, 189(1:1, 11, 3-BrPhS⁺).

Example 2

Preparation of 3-bromophenyl benzyl sulfide (2). 3-bromobenzenethiol (5g, 26.44 mmol) was added to a solution of sodium methoxide (1.43 g,26.48 mmol) in 20 ml of anhydrous methanol. The mixture was stirred for30 min at room temperature and a solution of benzyl bromide (4.53 g,26.48 mmol) in 20 ml anhydrous methanol was then added. The reactionmixture was stirred overnight at room temperature, poured into 2M oaqueous NaOH solution (40 ml) and extracted three times with ether (60ml×3). The combined organic layer was washed with saturated sodiumchloride solution and dried over anhydrous magnesium sulfate. Afterremoval of solvent, the product was purified by distillation at 161° C.,0.3 mmHg and isolated in 85.5% (6.31 g) yield. ¹H NMR (CDCl₃, 500 MHz) δppm: 4.12 (s, 2H, CH₂), 7.0-7.5 (m, 4H, Ar—H)GC-MS (relative intensity%): 278, 280 (1:1, 30.8, M⁺), 91(100, PhCH₂ ⁺).

Example 3

Preparation of 3-methylthiotriphenylamine (3). 3-bromothioanisole (1)(2.0 g, 9.85 mmol) was added to a solution oftris(dibenzylideneacetone)dipalladium (Pd₂(dba)₃) (0.28 g, 0.306 mmol)and bis(diphenylphosphino)ferrocene (IPPF) (0.245 g, 0.442 mmol) in drytoluene (20 mL) under a nitrogen atmosphere at room temperature. Theresultant mixture was stirred for 10 minutes. Sodium tert-butoxide (2.17g) and diphenylamnine (1.67 g, 9.85 mmol) were then added and stirred at90° C. for 24 h. The reaction mixture was poured into 20 mL of water,extracted three times with ether (3×60 mL) and dried over anhydrousmagnesium sulfate. The product was purified by flash columnchromatography using 2% ethyl acetate in hexanes as eluant to give 1.87g of a pale yellow oil (65.2%). The product was estimated to be greaterthan 95% pure by ¹H NMR and was used in next step without fiiierpurification. ¹H NMR (500 MHz, CDCl₃) δ ppm: 7.25 (t, br, J=7.5 Hz, 4H),7.14 (t, J=8.2 Hz, 1H), 7.08 (d, br, J=8.2 Hz, 4 H), 7.02 (t, br, J=7.5Hz, 2H), 6.97 (t, J=2.0 Hz, 1H), 6.87 (d, br, J=8.0, 1H), 6.82 (d, br,J=8.0, 1H), 2.20 (s, 3H, CH₃). ¹³C NMR (125 MHz, CDCl₃) δppm: 148.3,147.5, 139.3, 129.4. 129.2, 124.3, 122.9, 121.5, 120.5, 120.2, 15.6.EIMS (relative intensity %): 291(100, M⁺).

Example 4

Preparation of 3-benzylthiotriphenylamine (4). 3-bromophenyl benzylsulfide (3) (1.86 g, 6.67 mmol) was added to a solution oftris(dibenzylideneacetone)dipalladium (Pd₂(dba)₃) (0.15 g, 0.16 mmol)and bis(diphenylphosphino)ferrocene (DPPF) (0.11 g, 0.20 mmol) in drytoluene (20 mL) under nitrogen atmosphere at room temperature. Theresultant mixture was stirred for 10 minutes. Sodium tert-butoxide (1.42g) and diphenylamine (1.13 g, 6.69 mmol) were then added to thissolution and stirred at 90° C. for 24 h. The reaction mixture was pouredinto 20 mL of water, extracted three times with ether (3×60 mL) anddried over anhydrous magnesium sulfate. The product was purified byflash column chromatography using 2% ethyl acetate in hexanes as eluantto give 1.53 g of a pale yellow oil (62.5%). The product was estimatedto be greater than 95% pure by ¹H NMR and was used in next step withoutfinther purification. ¹H NMR (500 MHz, CDCl₃) δppm: 7.2-7.3 (m, overlap,9H), 7.10 (t, J=8.0 Hz, 1H), 7.0-7.06 (m, overlap, 7H), 6.93 (d, br,J=8.0 Hz, 1H), 6.86 (d, br, J=8.0 Hz, 1H), 4.04 (s, 2H, CH₂). ¹³C NMR(125 MHz, CDCl₃) δ ppm: 148.2, 147.4, 137.4, 137.2, 129.4, 129.2, 128.7,128.4, 127.1, 124.4, 123.4, 123.0, 121.6. 38.7 (One carbon was notobserved). EIMS (relative intensity %): 367 (100, M⁺).

Example 5

Preparation of [3-(N,N-diphenyl)amino]phenyl dimethyl sulfoniumtrifluoromethanesulfonate (5). 3-methylthiotriphenylamine (3) (1.77 g,6.08 mmol) was dissolved in 30 mL of dry methylene chloride and cooledto −78° C. in the dark. To this solution was added via syringe 0.76 mL(1.10 g, 6.70 mmol) of methyl trifluoromethanesulfonate under nitrogenand stirred for 30 minutes while the temperature was maintained at −78°C. The resultant mixture was then stirred overnight at room temperature.60 mL of ether was added to the mixture, resulting in the slow formationof white crystals. The crystals were collected by filtration and washedthree times with ether. The product was purified by recrystallizationfrom methylene chloride and ether at room temperature and isolated in2.45 g (88.6%) yield. ¹H NMR (500 MHz, d₆-DMSO) δ ppm: 7.61 (d, br,J=8.5 Hz, 1H), 7.58 (d, J=8.5 Hz, 1H), 7.55 (t, J=1.7 Hz, 1H), 7.38 (t,br, J=8.0 Hz, 4H), 7.13-7.20 (m, 3H), 7.09 (d, br, J=7.5, 4H), 3.19 (s,6H, CH₃). Anal. Calcd. for C₂₁H₂₀NO₃S₂F₃: C, 55.37; H, 4.42; N, 3.09.Found: C, 55.26; H, 4.59; N, 3.19.

Example 6

Preparation of [3-(N,N-diphenyl)amino]phenyl dimethyl sulfoniumhexafluorophosphate (7). A fresh 20 mL solution of KPF₆ (1.14 g, 5.98mmol) in water was added to a solution of [3-(N,N-diphenyl)amino]phenyldimethyl sulfonium trifluoromethanesulfonate (1.3 g, 2.86 mmol) in 15 mLof acetone. The mixture was stirred for 2 hours at room temperature inthe dark. The solid was collected by filtration and redissolved in 10 mLof acetone. This anion-exchange procedure was repeated three times. Theresultant white solid was washed three times with water and ether. Thesolid was purified by two precipitations from 10 mL of acetone solutionthrough the addition of 50 mL of diethyl ether. The final product yieldwas 1.08 g (83.6%). ¹H NMR (500 MHz, d₆-DMSO) δ pm: 7.62 (d, J=7.5 Hz,1H), 7.57 (d, J=8.0 Hz, 1H), 7.55 (s, 1H), 7.38 (t, br, J=8.2 Hz, 4H),7.13-7.20 (m, 3H, 7.09 (d, J=8.5, 4H), 3.19 (s, 6H, CH₃). Anal. Calcdfor C₂₀H₂₀NSF₆P: C, 53.22; H, 4.47; N, 3.10. Found: C, 53.20; H, 4.29;N, 3.13.

Example 7

Preparation of [3-(N,N-diphenyl)amino]phenyl dimethyl sulfoniumhexafluoroantimonate (8). A fresh 20 mL portion of NaSbF₆ (1.14 g, 4.40mmol) in water was added to a solution of [3-(N,N-diphenyl)amino]phenyldimethyl sulfonium trifluoromethanesulfonate (1.0 g, 2.19 mmol) in 10 mLof acetone. The mixture was stirred for 2 hours at room temperature inthe dark. The solid was collected by filtration and redissolved in 10 mLof acetone. The above anion-exchange was repeated three times. Theresulting white solid was washed three times with water and ether. Theproduct was purified by two precipitations from 10 mL of acetonesolution through the addition of 50 mL of diethyl ether. The finalproduct yield was 1.02 g (85.9%). ¹H NMR (500 MHz, d₆-DMSO) δppm: 7.62(d, J=7.5 Hz, 1H), 7.57 (d, J=8.0 Hz, 1H), 7.55 (s, 1H), 7.38 (t, br,J=8.2 Hz, 4H), 7.13-7.20 (m, overlap, 3H), 7.09 (d, J=8.5, 4H), 3.19 (s,6H, CH₃). Anal. Calcd for C₂₀H₂₀NSF₆Sb: C, 44.30; H, 3.72; N, 2.58.Found: C, 44.29; H, 3.76; N, 2.54.

Example 8

Preparation of [3-(N,N-diphenyl)amino]phenyl benzyl methyl sulfoniumhexafluoroantimonate (9). 3-Benzylthiotriphenylamine (1.48 g, 4.03 mmol)was dissolved in 30 mL of dry methylene chloride and cooled to −78 ° C.in the dark. To this solution was added via syringe 0.46 mL (0.67 g,4.07 mmol) of methyl trifluoromethanesulfonate under nitrogen. Themixture was then stirred for 30 minutes while the temperature wasmaintained at −78° C. The mixture was then allowed to warm to roomtemperature and was stirred overnight. 60 mL of ether was addedresulting in the formation of a light green oil. The solvent wasdecanted and the oil was dried in vacuo at room temperature. The productwas used in the ion-metathesis described below without furtherpurification.

A fresh 20 mL portion of aqueous NaSbF₆ (2.10 g, 8.11 mmol) was added toa solution of [3-(N,N-diphenyl)amino]phenyl benzyl methyl sulfoniumtrifluoromethane-sulfonate (6) (1.3 g, 2.86 mmol) in 10 mL of acetone.The mixture was stirred for 2 hours at room temperature in the dark. Thesolid was collected by filtration and redissolved in 10 mL of acetone.The above anion-exchange was repeated three times. The resultant whitesolid was washed three times with water and ether. The product waspurified by re-precipitation twice from 10 mL of acetone solution by theaddition of 50 mL diethyl ether giving a final yield of 1.08 g (71.8%).¹H NMR (500 MHz, CD₃COCD₃) δ ppm: 7.58-7.62 (m, overlap, 2H), 7.55 (t,J=7.7 Hz, 1H), 7.46 (t, J=7.5 Hz, 2H), 7.36 (t, J=7.7 Hz, 4H), 7.25-7.32(m, 4H), 7.17 (t, J=7.7 Hz, 2H), 7.02 (d, J=8.0, 4H), 5.25 (d, J=12.5Hz, 1H, CH₂), 5.02 (d, J=13.0 Hz, 1H, CH₂), 3.52 (s, 3H, CH₃). Anal.Calcd for C₂₆H₂₄NSF₆Sb: C, 50.51; H, 3.91; N, 2.26. Found: C, 50.42; H,3.98; N, 2.19.

Example 9

Preparation of trans-4,4′-dibromostilbene (10).¹⁴ 50% aqueous sodiumhydroxide (20 ml) was added to a solution of diethyl 4bromobenzylphosphnate (5.66 g, 18.4 mmol) and 4-bromobenzaldhyde (3.41 g, 18.4mmol) in benzene (20 ml). Tetra-(n-butyl) ammonium iodide (420 mg) wasadded and the mixture was refluxed under nitrogen for 30 min. Thereaction mixture was allowed to cool and diluted by addition of water(50 ml). A white solid was collected, washed with methanol and ether,and isolated in 51.0% (3.17 g) yield. ¹H NMR (CDCl₃, 500 MHz) δ ppm:7.48 (d, J=6.4 Hz, 4H), 7.37 (d, J=6.8 Hz, 4H), 7.02 (s, 2H, ═CH).

Example 10

Preparation of trans-4,4′-di(phenylamino)stilbene (11). To a solution oftris(di-benzylideneacetone)dipalladium (Pd₂(dba)₃) (0.335 g, 0.365 mmol)and bis-(diphenyl-phosphino)ferrocene (DPPF) (0.294 g, 0.530 mmol) indry toluene (30 ml) under nitrogen atmosphere was addedtrans-4,4′-dibromostilbene (10) (2.0 g, 5.91 mmol) at room temperature,and the resultant mixture was stirred for 10 min; sodium tert-butoxide(2.6 g) and aniline (1.102 g, 11.83 mmol) were added to this solutionand stirred at 90° C. overnight. The solid was collected, washed threetimes with methanol and ether and isolated in a yield of 87.8% (1.88 g)as an NMR-pure product. ¹H NM (CDCl₃, 500 MHz) δ ppm: 7.0-7.5 (m, 18H,Ar—H), 6.95 (s, 2H, ═CH), 5.77 (s, 2H, NH).

Example 11

Preparation of trans-4,4′-di(p-n-butylphenyl)aminostilbene (12). To asolution of tris(di-benzylideneacetone)dipalladium (Pd₂(dba)₃) (0.335 g,0.365 mmol) and bis-(diphenylphosphino)ferrocene (DPPF) (0.294 g, 0.530mmol) in dry toluene (20 ml) under nitrogen atmosphere was addedtrans-4,4′-dibromostilbene (10) (2.0 g, 5.91 mmol) at room temperature,and the resultant mixture was stirred for 10 min, sodium tert-butoxide(2.6 g) and 4-n-butyl aniline (1.77 g, 11.83 mmol) were added to thissolution and stirred at 90° C. overnight. The solid was collected,washed three times with methanol and ether, and isolated in 68.8% (1.93g) yield as an NAM-pure product. ¹H NMR (CDCl₃, 500 MHz) δ ppm: 7.38 (d,J=8.0 Hz, 4H), 7.10 (d, J=8.5 Hz, 4H), 7.03 (d, J=8.0 Hz, 4H), 7.0 (d,J=8.5 Hz, 4H), 6.91 (s, 2H, ═CH), 5.77 (s, 2H, NH), 2.56 (t, J=7.7 Hz,CH₂, 4H), 1.59 (m, CH₂, 4H), 1.37 (m, CH₂, 4H), 0.94 (t, J=7.5Hz, CH₃,6H).

Example 12

Preparation of trans-4,4′-di(N,N-phenylm-methylthiophenyl)amino-stilbene (13). To a solution oftris(dibenzylideneacetone) dipalladium (Pd₂(dba)₃) (0.14 g, 0.153 mmol)and bis(diphenylphosphino)ferrocene (DPPF) (0.12 g, 0.216 mmol) in drytoluene (10 ml) under a nitrogen atmosphere was added 3-bromothioanisole(1.0 g, 4.93 mmol) at room temperature, and the resultant mixture wasstirred for 10 min. Sodium tert-butoxide (1.08 g) andtrans-4,4′-diphenylaminostilbene (11) (0.89 g, 2.46 mmol) were added tothis solution and stirred at 90° C. overnight. The reaction mixture waspoured into water (20 ml), extracted three times with ether (30 ml×3)and dried over anhydrous magnesium sulfate. The yellow product waspurified by flash column chromatography using 5% ethyl acetate in hexaneas eluant and isolated in 25.5% (0.38 g) yield. ¹H NMR (CDCl₃, 500 MHz)δ ppm: 6.8-7.4 (m, 26H, Ar—H), 6.95 (s, 2H, ═CH), 2.40 (s, 6H, CH₃) ¹³CNMR (CDCl₃, 125.7 MHz) δppm: 148.0, 147.2, 146.7, 139.4, 132.1, 129.5,129.3, 127.1, 126.6, 124.6, 123.9, 123.2, 121.7, 120.8, 120.5, 15.6

Anal. Calcd. for C₄₀H₃₄ N₂S₂: C, 79.17; H, 5.65; N, 4.62. Found: C,78.84; H, 5.55; N, 4.54.

Example 13

Preparation of trans-4,4′-di(N,N-phenylm-benzylthiophenyl)amino-stilbene (14). To a solution oftris(dibenzylideneacetone)dipalladium (Pd₂(dba)₃) (0.111 g, 0.114 mmol)and bis-(diphenylphosphino)ferrocene (DPPF) (0.087 g, 0.157 mmol) in drytoluene (10 ml) under nitrogen atmosphere was added 3-bromophenyl benzylsulfide (1 g, 3.58 mmol) at room temperature, and the resultant mixturewas stirred for 10 min, sodium tert-butoxide (0.80 g), andtrans-4,4′-diphenylaminostilbene (11) (0.649 g, 1.79 mmol) were added tothis solution and stirred at 90° C. overnight. The reaction mixture waspoured into water (20 ml), extracted three times with ether (30 ml×3)and dried over anhydrous magnesium sulfate. The product was purified byflash column chromatography using 4% ethyl acetate in hexane as eluantand was isolated in 35.2% (0.48 g) yield. ¹H NMR (CDCl₃, 500 MHz) δ ppm:6.8-7.4 (m, 36H, Ar—H), 6.95 (s, 2H, ═CH), 4.02 (s, 4H, CH₂) ¹³C NMR(CDCl₃, 125.7 MHz) δ ppm: 148.0, 147.2, 146.7, 137.3, 132.1, 129.5,129.3, 128.7, 128.5, 127.2, 127.1, 126.7, 124.6, 124.0, 123.7, 123.2,121.9, 112.7, 38.69 (One carbon was not observed).

Example 14

Preparation oftrans-4,4′-di[N,N-(p-n-butylphenyl)m-methylthiophenyl]aminostilbene(15). To a solution of tris(dibenzylideneacetone) dipalladium(Pd₂(dba)₃) (0.197 g, 0.215 mmol) and bis(diphenylphosphino)ferrocene(DPPF) (0.156 g, 0.281 mmol) in dry toluene (10 ml) under nitrogenatmosphere was added 3-bromothioanisole (1.30 g, 6.40 mmol) at roomtemperature, and the resultant mixture was stirred for 10 min., sodiumtert-butoxide (1.41 g), and trans-4,4′-di-p-n-butylphenylaminostilbene(12) (1.52 g, 3.20 mmol) were added to this solution and stirred at 90°C. overnight. The reaction mixture was poured into water (20 ml),extracted three times with ether (30 ml×3) and dried over anhydrousmagnesium sulfate. The product was purified by flash columnchromatography using 3% ethyl acetate in hexanes as eluant,recrystallized from diethyl ether/hexnanes with slow evaporation ofether, and isolated in 30.2% (0.71 g) yield. ¹H NMR (CDCl₃, 500 MHz) δppm: 6.8-7.4 (m, 24H, Ar—H), 6.96 (s, 2H, ═CH), 2.59 (t, J=7.7 Hz, CH₂,4H), 2.40 (s, 6H, CH₃), 1.60 (m, CH₂, 4H), 1.38 (m, CH₂, 4H), 0.98 (t,J=7.5 Hz, CH₃, 6H) ¹³C NMR (CDCl₃, 125.7 MHz) δ ppm: 148.4, 147.1,144.9, 139.5, 138.5, 132.0, 129.6, 127.3, 126.7, 125.2, 123.7, 121.5,120.6, 120.3, 35.3, 33.9, 22.7, 15.9, 14.2 (one carbon was notobserved)HRMS (FAB): calcd. For C₄₈H₅₀N₂S₂M⁺718.3415, found 718.3404

Anal. Calcd. for C₄₈H₅₀ N₂S₂: C, 80.18 H, 7.01; N, 3.90. Found: C,80.02; H, 6.78; N, 4.17.

Example 15

Preparation of trans-4,4′-di(N,N-p-n-butylphenylm-benzylthiophenyl)aminostilbene (16). To a solution oftris(dibenzylideneacetone) dipalladium (Pd₂(dba)₃) (0.165 g, 0.180 mmol)and bis-(diphenylphosphino)ferrocene (DPPF) (0.131 g, 0.236 mmol) in drytoluene (10 ml) under nitrogen atmosphere was added 3-bromophenyl benzylsulfide (1.5 g, 5.38 mmol) at room temperature, and the resultantmixture was stirred for 10 min., sodium tert-butoxide (1.18 g), andtrans-4,4′-di-p-n-butylphenyl aminostilbene (12) (1.274 g, 2.69 mmol)were added to this solution and stirred at 90° C. overnight. Thereaction mixture was poured into water (20 ml), extracted three timeswith ether (20 ml) and dried over anhydrous magnesium sulfate. Theyellow product was purified by flash column chromatography twice using3% ethyl acetate in hexane as eluant and isolated in 41.2% (0.96 g)yield. ¹H NMR (CDCl₃, 500 MH) δ ppm: 6.8-7.4 (m, 34 Ar—H, 2 ═CH), 4.04(s, 4H, CH₂), 2.57 (t, J=7.7 Hz, CH₂, 4H), 1.60 (m, CH₂, 4H), 1.38 (m,CH₂, 4H), 0.94 (t, J=7.5 Hz, CH₃, 6H) ¹³C NMR (CDCl₃, 125.7 MHz) δ ppm:148.1, 146.8, 144.6, 138.3, 137.4, 137.2, 131.8, 129.4, 129.3, 128.7,128.4, 127.1, 127.0, 126.5, 125.0, 124.1, 123.5, 123.3, 121.4, 38.7,35.1, 33.6, 22.4, 14.0.

Example 16

Preparation of{3-[[4-(2-{4-[[3-(dimethylsulfonio)phenyl](phenyl)amino]-phenyl}-vinyl)phenyl](phenyl)amino]phenyl}(dimethyl)sulfoniumtriflate (17). Trans-4,4′-di(N,N-phenylm-methyllthiophenyl)aminostilbene (13) (0.2 g, 0.344 mmol) was dissolvedin 10 ml of dry methylene chloride and cooled at −78° C. in dryice-acetone bath. To this solution was added, via syringe, methyltrifluoromethanesulfonate (96.55 μl, 0.852 mmol) and the mixture wasstirred for 30 min while the temperature was maintained at −78° C. Theresultant mixture was stirred overnight at room temperature and thenpoured into 10 ml of ether. The product was precipitated as a yellowsolid, that was washed three times with ether and isolated in 95.8%(0.30 g) yield. ¹H NMR (DMSO, 500 MIlz) δ ppm: 7.0-7.8 (m, 26H, Ar—H),7.17 (s, ═CH, 2H), 3.40 (s, CH₃, 12H)

Anal. Calcd. for C₄₄H₄₀ N₂S₄: C, 56.52; H, 4.31; N, 3.00. Found: C,55.92; H, 4.36; N, 2.86.

Example 17

Preparation oftrans-benzyl{3-[[4-(2-{4-[[3-[benzyl(methyl)sulfonio)]phenyl](phenyl)amino]phenyl}vinyl)phenyl](phenyl)amino]phenyl}(methyl)sulfoniumtriflate (18). Trans-4,4′-di(N,N-phenyl-3-benzylthiophenyl)aminostilbene(14) (0.25 g, 0.329 mmol) was dissolved in 10 ml of dry methylenechloride and cooled at −78° C. in dry ice-acetone bath. To this solutionwas added, via syringe, methyl trifluoromethanesulfonate (82.7 μl, 0.731mmol) and the mixture was stirred for 30 min while the temperature wasmaintained at −78° C. The resultant mixture was then stirred overnightat room temperature and poured into 10 ml of ether. The product wasprecipitated as a yellow solid, that was washed three times with etherand isolated in 83.8% (0.31 g) yield. ¹H NMR (CD₃COCD₃, 500 MHz) δ ppm:6.9-7.8 (m, 38H, 36 Ar—H, 2═CH), 5.29 (d, ²J=12.5 Hz, 2H, SCH₂), 5.03(d, ²J=12.5 Hz, 2H, SCH₂), 3.29 (s, 6H, CH₃)¹³C NMR (CD₃COCD₃, 125.7MHz) δ ppm: 149.2, 146.1, 145.6, 133.7, 131.9, 130.7, 130.0, 129.9,129.3, 128.0, 127.8, 127.2, 127.0, 125.3, 124.9, 124.9, 123.9, 122.3,51.0, 24.5 (1 aryl carbon and 1 CF₃ carbon were not observed).

Example 18

[3-((4-butylphenyl){4-[2-(4-{(4-butylphenyl)[3-(dimethylsulfonio)phenyl]-amino}phenyl)vinyl]phenyl}amino)phenyl](dimethyl)sulfoniumtriflate (19).Trans-4,4′-di[(4-n-butylphenyl)(3-methylthiophenyl)amino]stilbene (15)(0.34 g, 0.47 mmol) was dissolved in 10 ml of dry methylene chloride andcooled at −78° C. in dry ice-acetone bath. To this solution was added,via syringe, methyl trifluoromethanesulfonate (96.55 μl, 0.852 mmol) andthe mixture was stirred for 30 min while the temperature was maintainedat −78° C. The resultant mixture was then stirred two days at roomtemperature. After removal of some solvent under reduced pressure, themixture was then poured into 20 ml of ether. The product wasprecipitated as a yellow solid, that was washed three times with etherand isolated in 75.5% (0.37 g) yield. ¹H NMR (CD₃COCD₃, 500 MHz) δ ppm:7.1-7.4 (mn, 24 Ar—H, 2 ═CH), 3.05 (s, 6H, CH₃,) 2.72 (t, J=7.7 Hz, CH₂,4H), 2.), 1.70 (m, CH₂, 4H), 1.46 (m, CH₂, 4H), 1.04 (t, J=7.3 Hz, CH₃,6H).

Example 19

Preparation oftrans-[3-((4-butylphenyl){4-[2-(4-{(4-butylphenyl)[3-((benzyl)methylsulfonio)phenyl]amino}phenyl)vinyl]phenyl}amino)phenyl]((benzyl)methyl)sulfoniumtriflate (20).Trans-4,4′-di[(4-n-butylphenyl)(3-benzylthiophenyl)amino]stilbene (16)(0.96 g, 1.103 mmol) was dissolved in 20 ml of dry methylene chlorideand cooled at −78° C. in dry ice-acetone bath. To this solution wasadded, via syringe, methyl trifluoromethanesulfonate (276 μl, 2.437mmol) and the mixture stirred for 30 min while the temperature wasmaintained at −78° C. The resultant mixture was then stirred two days atroom temperature. After removal of some solvent under reduced pressure,the mixture was then poured into 20 ml of ether. The product wasprecipitated as a yellow solid, that was washed three times with etherand isolated in 80.9% (1.07 g) yield. ¹H NMR (CD₃COCD₃, 500 MHz) δ ppm:6.9-7.8 (m, 34 Ar—H, 2 ═CH), 5.27 (d, ²J=12.5 Hz, 2H, SCH₂), 5.02 (d,²J=12.5 Hz, 2H, SCH₂), 3.53 (s, 6H, CH₃), 2.63 (t, J=7.7 Hz, CH₂, 4H),1.61 (m, CH₂, 4H), 1.36 (m, CH₂, 4H), 0.95 (t, J=7.2 Hz, CH₃, 6H)¹³C NMR(CD₃COCD₃, 125.7 MHz) δppm: 149.4, 145.6, 143.6, 139.9, 133.5, 131.8,130.7, 130.1, 129.8, 129.3, 127.9, 127.7, 127.1, 126.5, 125.7, 124.5,123.8, 123.4, 121.7, 51.0, 34.7, 33.5, 24.5, 22.1, 13.3. (One CF₃ carbonwas not observed).

Example 20

Preparation of{3-[[4-(2-{4-[[3-(dimethylsulfonio)phenyl](phenyl)amino]phenyl}vinyl)phenyl](phenyl)amino]phenyl}(dimethyl)sulfoniumhexafluoro-antimonate (21).trans-{3-[[4-(2-{4-[[3-(dimethylsulfonio)phenyl](phenyl)amino]phenyl}vinyl)phenyl](phenyl)amino]phenl}(dimethyl)sulfoniumtriflate (17) (0.3 g 0.33 mmol) was dissolved in methylene chloride (5ml) and acetone (10 ml). To this solution was added 10 ml aqueous sodiumhexafluoroantimonate solution (0.341 g, 1.32 mmol). The resultantmixture was stirred three days in the dark at room temperature with slowevaporation of methylene chloride and acetone, a yellow solid was formedand collected by filtration. The yellow solid was washed four times withwater and three times with ether. NMR-pure product was obtained withoutfurther purification in 75.4% (0.31 g) yield. ¹H NMR (DMSO, 500 MHz) δppm: 7.0-7.6 (m, 26H, Ar—H), 7.16 (s, ═CH, 2H), 3.35 (s, CH3, 12H) Anal.calcd for C₄₄H₄₀N₂S₂Sb₂F₁₂: C, 45.51; H, 3.64; N, 2.53; S, 5.78.

Found: C, 45.75; H, 3.70; N, 2.77; S, 5.94.

Example 21

Preparation oftrans-benzyl{3-[[4-(2-{4-[[3-[benzyl(methyl)sulfonio)]phenyl](phenyl)amino]-phenyl}-vinyl)phenyl](phenyl)amino]phenyl}(methyl)sulfoniumhexafluoroantimonate (22).trans-benzyl{3-[[4-(2-{4-[[3-[benzyl(methyl)sulfonio)]phenyl](phenyl)amino]-phenyl}-vinyl)phenyl](phenyl)amino]phenyl}(methyl)sulfoniumtriflate (18) (0.69 g, 0.74 mmol) was dissolved in acetone (10 ml). Tothis solution was added an aqueous solution of sodiumhexafluoroantimonate (0.76 g, 2.95 mmol). The resultant mixture wasstirred overnight in the dark at room temperature; with slow evaporationof acetone, a yellow oil was formed. The yellow oil was allowed to coolat 0° C. to become a yellow solid. The yellow solid was collected byfiltration and washed four times with water and three times with ether.A NMR-pure product was obtained without further purification and in77.4% (0.72 g) yield. ¹H NMR (CD₃COCD₃, 500 MHz) δ ppm: 6.9-7.6 (m, 38H,36 Ar—H, 2 ═CH), 5.26 (d, ²J=13.0 Hz, 2H, SCH₂), 5.02 (d, ²J=13.0 Hz,2H, SCH₂), 3.54 (s, 6H, CH₃)¹³C NMR (CD₃COCD₃, 125.7 MHz) δ ppm: 149.3,146.1, 145.6, 133.7, 131.9, 130.7, 130.1, 129.9, 129.3, 127.9, 127.8,127.2, 127.1, 125.3, 124.9, 124.8, 123.8, 122.2, 51.1,24.5 (One carbonwas not observed).

Example 22

Preparation of[3-((4-butylphenyl){4-[2-(4-{(4-butylphenyl)[3-(dimethyl-sulfonio)phenyl]amino}phenyl)vinyl]phenyl}amino)phenyl](dimethyl)sulfoniumhexafluoroantimonate (23). Trans-[3-((4-butylphenyl){4-[2-(4-{(4-butylphenyl)[3-(dimethylsulfonio)phenyl]amino}phenyl)vinyl]phenyl}amino)phenyl](dimethyl)sulfoniumtriflate (19) (0.87 g, 0.83 mmol) was dissolved in acetone (20 ml). Tothis solution was added 20 ml of an aqueous solution of sodiumhexafluoroantimonate (0.88 g, 3.40 mmol). The resultant mixture wasstirred two days in the dark at room temperature; with slow evaporationof acetone, a yellow solid was formed and collected by filtration. Theyellow solid was washed four times with water and three times withether. A NMR-pure product was obtained without further purification andisolated in 93.8% (0.95 g) yield. ¹H NMR (CD₃COCD₃, 500 MHz) δ ppm:7.1-7.4 (m, 24 Ar—H, 2 ═CH), 3.06 (s, 6H, CH₃,) 2.72 (t, J=7.7 Hz, CH₂,4H), 1.71 (m, CH₂, 4H), 1.46 (m, CH₂, 4H), 1.04 (t, J=7.3 Hz, CH₃, 6H)

Anal. calcd for C₅₀H₅₆N₂S₂Sb₂F₁₂: C, 49.20; H, 4.62; N, 2.29. Found: C,49.0; H, 4.57; N, 2.14.

Example 23

Preparation oftrans-[3-((4-butylphenyl){4-[2-(4-{(4-butylphenyl)[3-((benzyl)methylsulfonio)phenyl]amino}phenyl)vinyl]phenyl}amino)phenyl]((benzyl)methyl)sulfoniumhexafluoroantimonate (24).trans-[3-((4-butylphenyl){4-[2-(4-{(4-butylphenyl)[3-((benzyl)methylsulfonio)phenyl]amino}phenyl)vinyl]phenyl}amino)phenyl]((benzyl)methyl)sulfoniumtriflate (20) (0.85 g 0.81 mmol) was dissolved in acetone (10 ml). Tothis solution was added 10 ml of an aqueous solution of sodiumhexafluoroantimonate (0.84 g, 3.25 mmol). The resultant mixture wasstirred two days with slow evaporation of acetone in the dark at roomtemperature. The mixture was allowed to cool at 0° C., the yellow oilthat formed solidified. The yellow solid was collected by filtration andwashed four times with water and three times with ether. NMR-pureproduct was obtained without further purification in 83.2% yield (0.85g). ¹H NMR (CD₃COCD₃, 500 MHz) δ ppm: 6.9-7.7 (m, 36H, 34 Ar—H, 2 ═CH),5.27 (d, ²J=12.5 Hz, 2H, SCH₂), 5.02 (d, ²J=12.5 Hz, 2H, SCH₂), 3.52 (s,6H, CH₃), 2.63 (t, J=7.7 Hz, CH₂, 4H), 1.61 (m, CH₂, 4H), 1.36 (m, CH₂,4H), 0.95 (t, J=7.2 Hz, CH₃, 6H)¹³ C NMR (CD₃COCD₃, 125.7 MHz) δppm:149.3, 145.6, 143.5, 139.9, 133.5, 131.9, 130.7, 130.0, 129.8, 129.3,127.9, 127.7, 127.1, 126.5, 125.6, 124.5, 123.8, 123.4, 121.7, 51.0,34.7, 33.5, 24.5, 22.1, 13.3.

Example 24

Preparation of tetraethyl p-xylylenebisphosphonate (25) (Piechucki, C.Synthesis, 1976, 187). A mixture of α,α′-dichloro-p-xylene (20 g, 0.114mol) and triethyl phosphite (60 ml) was refluxed at 180° C. overnight.80 ml of hexanes was added, and white crystals were formed immediately.Then the mixture was cooled at 0° C., and the product was collected,washed three times with 40 ml of hexanes and isolated in 94.4% (40.8 g)yield.

Example 25

Preparation of E,E-1,4-Bis(p-bromostyryl)benzene (26). 50% aqueoussodium hydroxide (20 ml) was added to a solution of tetraethylp-xylylenebisphosphonate (2.40 g, 6.35 mmol) (25) and4-bromobenzaldehyde (2.41 g, 13.02 mmol) in 10 ml of benzene.Tetra-n-butylammonium iodide (148 mmg) was added and the mixture wasrefluxed under nitrogen for 1 hour. The reaction mixture was allowed tocool and diluted by the addition of water (25 ml). A yellow solid wascollected and washed three times with water, methanol and ether. Theproduct was purified by recrystallization from xylenes and was isolatedin 61.9% (1.73 g) yield (Product is insoluble in standard solvents).

Example 26

Preparation of E,E-1,4-Bis[p-(N-4′-n-butylphenyl)aminostyryl]benzene(27). To a solution of tris(dibenzylideneacetone) dipalladium(Pd₂(dba)₃) (0.17 g, 0.185 mmol) and bis(diphenylphospino)ferrocene(DPPF) (0.13 g, 0.235 mmol) was dissolved in 40 ml of toluene was addedE,E-1,4-bis(p-bromostyryl)benzene (26) (4.06 g, 9.23 mmol) at roomtemperature under nitrogen, the resultant mixture was stirred for 10minutes, and sodium tert-butoxide (4.80 g) and 4-butylaniline (2.76 g,18.49 mmol) were added to this solution. The mixture was then stirred at90° C. overnight. A yellow solid was collected, washed three times withmethanol and ether, and was isolated in 71.8% (3.79 g) yield (Product isinsoluble in standard solvents).

Example 27

Preparation ofE,E-1,4-Bis{p-[N-(4-n-butylphenyl)-N-(3-methylthiophenyl)]aminostyryl}benzene(28). To a solution of tris(dibenzylideneacetone) dipalladium(Pd₂(dba)₃) (0.068 g, 0.074 mmol) and bis(diphenylphospino)ferrocene(DPPF) (0.049 g, 0.088 mmol) in 20 ml of toluene was added3-bromothioanisole (1.50 g, 7.39 mmol) at room temperature undernitrogen, the resultant mixture was stirred for 10 minutes, sodiumtert-butoxide (1.95 g) andE,E-1,4-Bis[p-(N-p-butylphenyl)aminostyryl]benzene (27) (2.11 g, 3.69mmol) were added to this solution which was then stirred for 20 h at 90°C. The mixture was allowed to cool, poured into 20 ml of water andextracted three times with ether (60 ml×3). The combined organic layerwas dried over anhydrous magnesium sulfate. After removal of solventunder reduced pressure, the product was purified by flash columnchromatography using 5% of ethyl acetate in hexanes as eluant. Theproduct was further purified by recrystallization from the mixturesolvent of ether and hexanes (1:5) and was isolated in 9.2% (0.28 g)yield. ¹H NMR (CDCl₃, 500 MHz) δppm: 6.8-7.5 (m, 32 H, 28 ArH, 4 ═CH),2.59 (t, J=7.5 Hz, 4H, CH₂), 2.41 (s, 6H, SCH₃), 1.62 (m, 4H, CH₂), 1.39(m, 4H, CH₂), 0.96 (t, J=7.0 Hz, 6H, CH₃)¹³C NMR (CDCl₃, 125.7 MHz) δppm: 148.1, 147.2, 144.7, 139.3, 138.4, 136.6, 131.4, 129.4, 129.3,127.8, 127.3, 126.6, 125.1, 123.3, 121.4, 120.5, 120.2, 35.1, 33.6,22.4, 15.6, 14.0 (One carbon was not observed) HRMS (FAB) calcd. forC₅₆H₅₆N₂S₂ M⁺820.3885; found 820.3917.

Example 28

Preparation ofE,E-1,4-Bis{p-[N-(4-n-butylphenyl)-N-(3-benzylthiophenyl)]aminostyryl}benzene(29). To a solution of tris(dibenzylideneacetone) dipalladium(Pd₂(dba)₃) (0.039 g, 0.041 mmol) and bis(diphenylphospino)ferrocene(DPPF) (0.027 g, 0.049 mmol) in 10 ml of toluene was added 3-bromophenylbenzyl sulfide (1.13 g, 4.06 mmol) at room temperature under nitrogen,the resultant mixture was stirred for 10 minutes, sodium tert-butoxide(0.89 g) and E,E-1,4-Bis[p-(N-p-butylphenyl)aminostyryl]benzene (27)(1.16 g, 2.03 mmol) were added to this solution and then stirred for 20h at 90° C. The mixture was allowed to cool, poured into 20 ml of waterand extracted three times (30 ml×3) with ether. The combined organiclayer was dried over anhydrous magnesium sulfate. After removal ofsolvent under reduced pressure, the product was purified by flash columnchromatography using 6% of ethyl acetate in hexanes as eluant and wasisolated in 16.2% (0.32 g) yield. ¹H NMR (CDCl₃, 500 MHz) δ ppm: 6.8-7.7(m, 42 H, 38 ArH, 4 ═CH), 4.00 (s, 4H, SCH₂), 2.57 (t, J=7.5 Hz, 4H,CH₂), 1.60 (m, 4H, CH₂), 1.39 (m, 4H, CH₂), 0.98 (t, J=7.2 Hz, 6H,CH₃)¹³C NMR (CDCl₃, 125.7 MHz) δppm: 148.0, 147.0, 144.5, 138.3, 137.3,137.2, 136.6, 131.3, 129.4, 129.3, 128.7, 128.4, 127.8, 127.2, 127.0,126.5, 125.0, 124.1, 123.3, 123.2, 121.5, 38.5, 35.0, 33.6, 22.4, 14.0(One carbon was not observed) HRMS (FAB) Calcd. for C₆₈H₆₄N₂S₂M⁺972.4511, found 972.4519.

Example 29

Preparation of 3-methylthio-4′-butyl diphenyl amine (30). To a solutionof tris(dibenzylideneacetone)dipalladium (Pd₂(dba)₃) (0.18 g, 0.196mmol) and bis(diphenylphospino)ferrocene (DPPF) (0.13 g, 0.235 mmol) in100 ml of dry toluene was added 3-bromothioanisole (4.0 g, 0.0197 mol)at room temperature under nitrogen, the resultant mixture was stirredfor 10 minutes, sodium tert-butoxide (4.30 g) and 4-n-butylamine (3.10g, 0.0201 mol) were added to this solution and stirred at 90° C.overnight. The mixture was poured into 100 ml of water and extractedthree times with ether (100 ml×3). The combined organic layer was driedover magnesium sulfate. After removal of solvent, the product waspurified by flash column chromotography using 10% of ethyl acetate inhexanes as eluant and was isolated in 78.4% (4.20 g) yield. ¹H NMR(CDCl₃, 500 MHz) δppm: 7.13 (t, J=8.0 Hz, 1 H), 7.08 (d, J=8.0 Hz, 2 H),7.00 (d, J=8.5 Hz, 2 H), 6.89 (s, 1H), 6.75 (m, 2H), 5.60 (s, 1H, NH),2.56 (t, J=7.7 Hz, 2 H, CH₂), 2.43 (s, 3H, SCH₃), 1.58 (m, 2H, CH₂),1.35 (m, 2H, CH₂), 0.93 (t, J=7.2 Hz, 3H, CH₃) GC-MS (relative intenstiy%): 271 (M+, 67.8), 228 (m-MeSPh-NH-PhCH₂ ⁺, 100).

Example 30

Preparation of 3-benzylthio-4′-butyl diphenyl amine (31). To a solutionof tris(dibenzylideneacetone)dipalladium (Pd₂(dba)₃) (0.14 g, 0.153mmol) and bis(diphenylphospino)ferrocene (DPPF) (0.12 g, 0.217 mmol) in100 ml of dry toluene was added 3-bromophenyl benzyl sulfide (4.06 g,0.0150 mol) at room temperature under nitrogen, the resultant mixturewas stirred for 10 minutes, sodium tert-butoxide (3.27 g) and4-butylaniline (3.50 g, 0.0234 mol) were added to this solution andstirred at 90° C. under nitrogen for 20 hours. The mixture was thenpoured into 100 ml of water and extracted three times with ether (100ml×3). The combined organic layer was dried over magnesium sulfate.After removal of solvent, the product was purified by flash columnchromotography using 10% of ethyl acetate in hexanes as eluant and wasisolated in 83.3% (4.33 g) yield. ¹H NMR (CDCl₃, 500 MHz) δ ppm: 7.26(m, 6H), 7.12 (t, J=8.0 Hz 1 H), 7.07 (d, J=8.0 Hz, 2H), 6.94 (d, J=8.5Hz, 2 H), 6.82 (d, J=7.5 Hz, 1H), 6.79(d, J=8.0 Hz 1H), 5.59 (s, 1H,NH), 4.04 (s, 2H, SCH₂), 2.58 (t, J=7.7 Hz, 2 H, CH₂), 1.59 (m, 2H,CH₂), 1.38 (m, 2H, CH₂), 0.96 (t, J=7.2 Hz, 3H, CH₃) GC-MS (relativeintensity %): 347 (M⁺, 100), 304 (m-PhCH₂SPh-NH-Ph-p-CH₂ ⁺, 100).

Example 31

Preparation of 2-p-bromophenyl-1,3-dioxolanes (32) (Greene, T.; Wuts, P.G. Protective Groups in Organic Synthesis, 2^(nd) Edition, John-Wiley&Sons, 1991, p 185). p-Toluenesulfonic acid (200 mg) was added to amixture of 4-bromobenzaldhyde (20 g, 0.108 mol) and ethylene glycol (18ml, 0.323 mol) in toluene (250 ml). The mixture was heated to reflux for20 hours with removal of water from the reaction. Then the mixture wasallowed to cool, washed three times by aqueous NaHCO₃ and dried overanhydrous Na₂SO₄. After removal of solvent, the product wasrecrystallized from pentane and was isolated in 85.7% (21.2 g) yield.

Example 32

Preparation of 3-methylthio-4′-butyl-4″-formyl triphenyl amine (35). Toa solution of tris(dibenzylideneacetone)dipalladium (Pd₂(dba)₃) (0.14 g,0.153 mmol) and bis(diphenylphospino)ferrocene (DPPF) (0.11 g, 0.198mmol) in 60 ml of toluene was added 2-p-bromophenyl-1,3-dioxolane (32)(5.22 g, 0.0228 mol) at room temperature under nitrogen, the resultantmixture was stirred for 10 minutes, sodium tert-butoxide (3.34 g) and3-methylthio-4′-butyldiphenlylamine (30) (4.12 g, 0.0152 mol) were andstired at 90° C. under nitrogen for 20 hours. The mixture was pouredinto 100 ml of water and extracted three times with ether (100 ml×3).The combined organic layer was dried over magnesium sulfate. Afterremoval of solvent, the residue was dissolved in THF (70 ml), 2 M ofaqueous HCl solution (30 ml) was added and the mixture was stirred for 1hour. Then 1 M aqueous sodium hydroxide solution (70 ml) was added andthe mixture was extracted three times with ether (120 ml×3). Thecombined organic layer was dried over magnesium sulfate. After removalof the solvent, the product was purified by flash column chromatographyusing 10% of ethyl acetate in hexanes and was isolated in 78.8% (4.41 g)yield. ¹H NMR (CDCl₃, 500 MHz) δ ppm: 7.67 (d, J=8.5 Hz, 2H), 7.23 (t,J=8.0 Hz, 1 H), 7.15 (d, J=8.0 Hz, 2 H), 7.07 (d, J=8.5 Hz, 2 H),7.01-7.06 (m, 2H), 7.0 (d, J=9.0 Hz 2H), 6.91 (d, J=8.0 Hz, 1H), 2.60(t, J=7.7 Hz, 2 H, CH₂), 2.42 (s, 3H, SCH₃), 1.61 (m, 2H, CH₂), 1.38 (m,2H, CH₂), 0.94 (t, J=7.2 Hz, 3H, CH₃) ¹³C NMR (CDCl₃, 125.7 MHz) δ ppm:190.4, 153.3, 146.6, 143.2, 140.3, 140.1, 131.3, 129.9, 129.7, 128.9,126.4, 123.5, 122.5, 122.4, 119.1, 35.1, 33.5, 22.4, 15.5, 14.0GC-MS(relative intenstiy %): 375 (M⁺, 90.3), 332 (m-MeSPh-N-p-PhCHO)-p-PhCH₂⁺, 100) Anal. Calcd. for C₂₄H₂₅ NOS: C, 76.76; H, 6.71; N, 3.73. Found:C, 77.04; H, 6.56; N, 3.85.

Example 33

Preparation of 3-benzylthio-4′-butyl-4″-formyl triphenyl amine (36). Toa solution of tris(dibenzylideneacetone)dipalladium (Pd₂(dba)₃) (0.14 g,0.153 mmol) and bis(diphenylphospino)ferrocene (DPPF) (0.11 g, 0.198mmol) in 50 ml of toluene was added 2-p-bromophenyl-1,3-dioxolane (32)(5.22 g, 0.0228 mol) at room temperature under nitrogen, the resultantmixture was stirred for 10 minutes, sodium tert-butoxide (2.80 g) and3-benzylthio-4′-butyldiphenlylamine (31) (4.33 g, 0.0125 mol) were addedand the mixture was stirred at 90° C. under nitrogen for 20 hours. Thenthe mixture was poured into 100 ml of water and extracted three timeswith ether (100 ml×3). The combined organic layers were dried overmagnesium sulfate. After removal of solvent, the residue was dissolvedin THF (60 ml), 2 M of aqueous HCl solution (30 ml) was then added andthe mixture was stirred for 1 hour. 1 M of aqueous sodium hydroxidesolution (70 ml) was added and the mixture was extracted three timeswith ether (120 ml×3). The combined organic layers were dried overmagnesium sulfate. After removal the solvent, the product was purifiedby flash column chromatography using 10% of ethyl acetate in hexanes andwas isolated in 73.8% (4.16 g) yield.¹H NMR (CDCl₃, 500 MHz) δ ppm: 7.65(d, J=9.0 Hz, 2H), 7.18-7.30 (m, 6H), 7.15 (d, J=8.5 Hz, 2H), 7.09 (d,J=7.5 Hz, 2 H), 7.03 (d, J=8.5 Hz, 2H), 7.0 (d, J=9.0 Hz 2H), 6.95 (d,J=8.5 Hz, 1H), 6.92 (d, J=8.5 Hz, 2H), 4.04 (s, 2H, SCH₂), 2.62 (t,J=7.7 Hz, 2 H, CH₂), 1.62 (m, 2H, CH₂), 1.40 (m, 2H, CH₂), 0.96 (t,J=7.2 Hz, 3H, CH₃) ¹³C NMR (CDCl₃, 125.7 MHz) δ ppm: 190.4, 153.2,146.6, 143.2, 140.3, 137.8, 137.0, 131.3, 129.9, 129.7, 128.9, 128.7,128.5, 127.2, 126.6, 126.4, 125.7, 123.6, 119.1, 38.6, 35.1, 33.5, 22.4,14.OGC-MS (relative intenstiy %): 451 (M⁺, 100), 408(m-PhCH₂SPh-N-p-PhCHO)-p-PhCH₂ ⁺, 50) Anal. Calcd. for C₃₀H₂₉ NOS: C,79.78; H, 6.47; N, 3.10. Found: C, 79.95; H, 6.61; N, 3.28.

Example 34

Preparation ofE,E-1,4-Bis[4′-(N-p-^(n)butylphenyl-N-m-methylthiophenyl)aminostyryl]benzene(37). To a solution of 3-methylthio-4′-butyl-4″-formyl triphenyl amine(35) (2.0 g, 5.33. mmol) and tetraethyl α,α′-p-xylenebisphosphonate (25)(0.98 g, 2.59 mmol) in dry THF (30 ml) at 0° C. was added 6.0 ml of 1 Msolution of KO^(t)Bu in THF. After 2 hours the reaction was quenched byaddition of 30 ml of water, a large amount of yellow precipitate wasformed. After removal THF under reduced pressure, the yellow solid wascollected by filtration. The product was purified by flashchromatography using ethyl acetate/methylene chloride/hexanes (1:10:10)as eluant and was isolated in 95.0% (2.08 g) yield.¹H NMR (CDCl₃, 500MHz) δ ppm: 6.8-7.5 (m, 32 H, 28 ArH, 4 ═CH), 2.59 (t, J=7.5 Hz, 4H,CH₂), 2.41 (s, 6H, SCH₃), 1.62 (m, 4H, CH₂), 1.39 (m, 4H, CH₂), 0.96 (t,J=7.0 Hz, 6H, CH₃)¹³C NMR (CDCl₃, 125.7 MHz) δ ppm: 148.1, 147.2, 144.7,139.3, 138.4, 136.6, 131.4, 129.4, 129.3, 127.8, 127.3, 126.6, 125.1,123.3, 121.4, 120.5, 120.2, 35.1, 33.6, 22.4, 15.6, 14.0 (One carbon wasnot observed) HRMS (FAB) calcd. for C₅₆H₅₆N₂S₂M⁺820.3885; found 820.3917

Anal. Calcd. for C₅₆H₅₆ N₂S₂: C, 81.91; H, 6.87; N, 3.41. Found: C,81.98; H, 7.10; N, 3.54.

Example 35

Preparation ofE,E-1,4-Bis[4′-p-^(n)butylphenyl-N-m-benzylthiophenyl)aminostyryl]benzene(38). To a solution of 3-methylthio-4′-butyl-4″-formyl triphenyl amine(36) (2.0 g, 4.43 mmol) and tetraethyl α,α′-p-xylenebisphosphonate (25)(0.82 g, 2.17 mmol) in dry THF (30 ml) at 0° C. was added 5.0 ml of 1 Msolution of KO^(t)Bu in THF. After 2 hour the reaction was quenched byaddition of 30 ml of water, then 25 ml of saturated brine was added andthe mixture was extracted three times with methylene chloride/ether(1:4) (3×100 ml). The combined organic layer was dried over magnesiumsulfate. After removal of solvent, the product was purified by flashcolumn chromatography using 10% of ethyl acetate in hexanes as eluantand was isolated in 94.7% (2.21 g) yield. ¹H NMR (CDCl₃, 500 MHz) δ ppm:6.8-7.7 (m, 42 H, 38 Ar—H, 4 ═CH), 4.00 (s, 4H, SCH₂), 2.57 (t, J=7.5Hz, 4H, CH2), 1.60 (m, 4H, CH₂), 1.39 (m, 4H, CH₂), 0.98 (t, J=7.2 Hz,6H, CH₃)¹³C NMR (CDCl₃, 125.7 MHz) δ ppm: 148.0, 147.0, 144.5, 138.3,137.3, 137.2, 136.6, 131.3, 129.4, 129.3, 128.7, 128.4, 127.8, 127.2,127.0, 126.5, 125.0, 124.1, 123.3, 123.2, 121.5, 38.5, 35.0, 33.6, 22.4,14.0 (One carbon was not observed.

HRMS (FAB) calcd. for C₆₈H₆₄N₂S₂ M⁺972.4511; found 972.4519

Anal. Calcd. for C₆₈H₆₄ N₂S₂: C, 84.08; H, 7.43; N, 2.58. Found: C,83.80; H, 7.66; N, 2.77.

Example 36

Preparation ofE;E-(3-{(4-butylphenyl)[4-(2-{4-12-(4-{(4-butylphenyl)[3-(dimethylsulfonio)phenyl]amino}phenyl)vinyl]phenyl}vinyl)phenyl]amino}phenyl)(dimethyl)sulfonium(41).E,E-1,4-Bis{p-[N-(4-n-butylphenyl)-N-(3-methylthiophenyl)]aminostyryl}benzene(37) (0.27 g, 0.33 mmol) was dissolved in 10 ml of dry methylenechloride and cooled at −78° C. To this solution was added via syringemethyl trifluoromethanesulfonate (82.7 μl, 0.73 mmol) and stirred for 30min while the temperature was maintained at −78° C. Then the mixture wasstirred for two hours at room temperature. The solvent was removed underreduced pressure, and metathesis of anion was performed withoutisolation of the product.

The residue was dissolved in acetone (10 ml) and 10 ml of NaSbF₆ (0.35g, 1.35 mmol) aqueous solution was added. The mixture was stirred for 4hours and acetone was removed under reduced pressure at roomtemperature. A yellow solid was collected by filtration. Thisanion-exchange procedure was repeated three times. The yellow solid wascollected, washed four times with water, and then dissolved in smallamount of acetone (∞1 ml). To this solution 20 ml of ether was added anda yellow precipitate was formed immediately. The yellow solid was washedthree times with ether, dried under vacuum and was isolated in 62.2%(0.27 g) yield.¹H NMR (CD₃COCD₃, 500 MHz) δppm: 7.0-7.8 (m, 32 H, 28ArH, 4 ═CH), 3.44 (s, 12H, CH₃), 2.64 (t, J=7.5 Hz, 4H, CH₂), 1.62 (m,4H, CH₂), 1.39 (m, 4H, CH₂), 0.94 (t, J=7.5 Hz, 6H, CH₃)

Anal. Calcd. for C₅₈H₆₂ N₂S₂F₁₂Sb₂: C, 52.67; H, 4.72; N, 2.12. Found:C, 52.43; H, 4.69; N, 2.08.

Example 37

Preparation ofE,E-benzyl{3-[(4-{2-[4-(2-{4-[{3-[benzyl(methyl)sulfonio]phenyl}(4-butylphenyl)amino]phenyl}vinyl)phenyl]vinyl}phenyl)(4-butylphenyl)amino]phenyl}methylsulfoniumhexafluoroantimonate (42).E,E-1,4-Bis{p-[N-(4-n-butylphenyl)-N-(3-benzylthio phenyl)]aminostyryl}benzene (38) (0.59 g, 0.61 mmol) was dissolved in 10 ml of drymethylene chloride and cooled at −78° C. To this solution was added viasyringe methyl trifluoromethanesulfonate (145 μl, 1.28 mmol). Whilemaintaining that temperature, the mixture was stirred for 30 min. Thenthe mixture was stirred for two days at room temperature. The solventwas removed under reduced pressure and, metathesis of anion wasperformed without isolation of the product.

The residue was dissolved in acetone (10 ml) and 10 ml of NaSbF₆ (0.70g, 2.70 mmol) aqueous solution was added. Then the mixture was stirredfor 4 hours and acetone was removed under reduced pressure at roomtemperature. The yellow solid was collected by filtration. The aboveanion-exchange procedure was repeated three times. The yellow solid wascollected, washed four times with water, and then dissolved in smallamount of acetone (˜1 ml). To this solution was added 20 ml of ether anda yellow precipitate was formed. The yellow solid was washed three timeswith ether, dried under vacuum and was isolated in 70.6% (0.63 g).

Example 38

Preparation of 4,4′-di-n-butyl-3″-methylthiotriphenylamine (44). To asolution of tris(dibenzylideneacetone)dipalladium (Pd₂(dba)₃) (0.11 g,0.120 mmol) and bis(diphenylphospino)ferrocene (DPPF) (0.082 g, 0.147mmol) in 20 ml of dry toluene was added 3-bromothioanisole (1) (2.5 g,12.31 mmol) at room temperature under nitrogen, the resultant mixturewas stirred for 10 minutes, sodium tert-butoxide (2.70 g)Bi-(4-n-butylphenyl)amine (43) (3.46 g, 10.31 mmol) were added to thissolution and stirred for 20 h at 90° C. The mixture was allowed to cool,poured into 50 ml of water and extracted three times (60 ml×3) withether. The combined organic layer was dried over anhydrous magnesiumsulfate. After removal of solvent under reduced pressure, the productwas purified by flash column chromatography using 10% of ethyl acetatein hexanes as eluant and was isolated in 94.9% (4.71 g) yield. ¹H NMR(CDCl₃, 500 MHz) δppm: 6.7-7.2 (m, 12H, ArH), 2.57 (t, J=7.5 Hz, 2H,CH₂), 2.4 (s, 3H, SCH₃), 1.60 (m, 2H, CH₂), 1.39 (m, 2H, CH₂), 0.95 (t,J=8.0 Hz, 3H, CH₃)EIMS (relative intensity %): 403 (M⁺, 100).

Example 39

Preparation of 4,4′-di-n-butyl-3″-benzylthiotriphenylamine (45). To asolution of tris(dibenzylideneacetone)dipalladium (Pd₂(dba)₃) (0.079 g,0.086 mmol) and bis(diphenylphospino)ferrocene (DPPF) (0.064 g, 0.116mmol) in 20 ml of dry toluene was added 3-bromophenyl benzyl sulfide (2)(3.0 g, 10.75 mmol) at room temperature under nitrogen, the resultantmixture was stirred for 10 minutes, sodium tert-butoxide (2.36 g)Bi-(4-n-butylphenyl)amine (2.42 g, 10.75 mmol) were added to thissolution and stirred for 20 h at 90° C. The mixture was allowed to cool,poured into 50 ml of water and was extracted three times (60 ml×3) withether. The combined organic layer was dried over anhydrous magnesiumsulfate. After removal of solvent under reduced pressure, the productwas purified by flash column chromatography using 8% of ethyl acetate inhexanes as eluant and was isolated in 66.4% (3.29 g) yield.

Example 40

Preparation of 4-[di-(p-^(n)butylphenyl)amino]-2-methylthiobenzaldehyde(46). To a solution of 4,4′-di-n-butyl-3″-methylthiotriphenylamine (44)(4.59 g, 11.38 mmol) and DMF (40 ml) at 0° C. was added POCl₃ (1.90 g,12.40 mmol) dropwise. The resulting mixture was stirred at 95-100° C.under nitrogen for 20 hours. The mixture was cooled, poured into 50 mlof ice water slowly, neutralized with 4 M aqueous NaOH and extractedthree times (40 ml×3) with ether. The combined organic layer was washedwith saturated brine and dried over magnesium sulfate. After removal ofsolvent, the product was purified by flash chromatography using 10% ofethyl acetate in hexanes as eluant and was isolated in 63.9% (3.14 g)yield.¹H NMR (CDCl₃, 500 MHz) δppm: 9.99 (s, 1H, CHO), 7.55 (d, J=8.5Hz, 1 H), 7.16 (d, J=8.5 Hz, 4H), 6.98 (d, J=8.5 Hz, 4 H), 6.71 (s, br,1H), 6.68 (d, br, J=8.5 Hz, 1 H), 2.60 (t, J=7.7 Hz, 4H, CH₂), 2.17 (s,3H, CH₃), 1.61 (m, 4H, CH₂), 1.38 (m, 4H, CH₂), 0.94 (t, J=7.5 Hz, 6H,CH₃)¹³C NMR (CDCl₃, 125.7 MHz) δppm: 189.2, 153.0, 144.6, 143.2, 1430.3,135.1, 129.6, 126.4, 124.8, 114.0, 35.1, 33.5, 22.3, 14.9, 14.0 (Onecarbon was not observed)GC-MS (relative intensity %): 431 (M⁺, 100)

Anal. Calcd. for C₂₈H₃₃ NOS: C, 77.91; H, 7.71; N, 3.25. Found: C,77.91; H, 7.79; N, 3.45.

Example 41

Preparation of 4-[di-(p-^(n)butylphenyl)amino]-2-benzylthiobenzaldehyde(47). To a solution of 4,4′-di-n-butyl-3″-benzyltriphenylamine (45)(3.42 g, 7.14 mmol) and DMF (25 ml) at 0° C. was added POCl₃ (1.20 g,7.85 mmol) dropwise. The resulting mixture was stirred at 95-100° C.under nitrogen for 20 hours. The mixture was cooled, poured into 40 mlof ice water slowly, neutralized with 4 M aqueous NaOH and extractedthree times (40 ml×3) with ether. The combined organic layer was washedwith saturated brine and dried over magnesium sulfate. After removal ofsolvent, the product was purified by flash chromatography using 10% ofethyl acetate in hexanes as eluant and was isolated in 64.9% (2.35 g)yield. ¹H NMR (CDCl₃, 500 MHz) δpp m: 10.01(s, 1H, CHO), 7.56 (d, J=8.5Hz, 1 H), 7.21 (m, 3H), 7.16 (d, J=8.5 Hz, 4H), 7.09 (m, 2H), 7.03 (d,J=8.5 Hz, 4 H), 6.81 (s, br, 1H), 6.69 (d, br, J=8.5 Hz, 1 H), 3.88 (s,2H, SCH₂), 2.61 (t, J=7.7 Hz, 4H, CH₂), 1.61 (m, 4H, CH₂), 1.38 (m, 4H,CH₂), 0.94 (t, J=7.5 Hz, 6H, CH₃)¹³C NMR (CDCl₃, 125.7 MHz) δ ppm:189.4, 152.9, 143.1, 142.8, 140.3, 136.4, 134.0, 129.6, 128.7, 128.5,127.1, 126.5, 125.6, 116.6, 114.9, 37.6, 35.1, 33.5, 22.4, 14.0.

Example 42

Preparation ofE,E-1,4-Bis[2′-methylthio-4′-(N,N-di-p-n-butylphenyl)aminostyryl]benzene(48). To a solution of of 4-(N,N-di-p-n-butylphenyl)amino-2-methylthiobenzaldehyde (46) (1.50 g, 3.48 mmol) and tetraethylα,α′-p-xylenebisphosphonate (25) (0.65 g, 1.72 mmol) in dry THF (20 ml)at 0° C. was added 5.0 ml of 1 M solution of KO^(t)Bu in THF. After 2hours the reaction was quenched by addition of 25 ml of water, then 25ml saturated brine was added and the mixture was extracted three timesby methylene chloride/ether (1:4) (3×60 ml). The combined organic layerwas dried over magnesium sulfate. After removal of solvent, the productwas purified by flash chromatography using 9% of ethyl acetate inhexanes as eluant and was isolated in 87.5% (1.43 g) yield (including˜6% of E-Z and/or Z-Z isomers by NMR). The products were dissolved intoluene (30 ml) and a small iodine crystal was added to this solution.The solution was refluxed overnight. After removal of solvent, theproduct was purified by flash chromatography using 7% of ethyl acetatein hexanes as eluant. ¹H NMR (CDCl₃, 500 MHz) δppm: 6.8-7.6 (m, 30H),2.58 (t, J=7.5 Hz, 8H, CH₂), 2.28 (s, 6H, CH₃), 1.60 (m, 8H, CH₂), 1.38(m, 8H, CH₂), 0.95 (t, J=7.0 Hz, 12H, CH3)13C NMR (CDCl3, 125.7 MHz)δppm: 148.0, 144.9, 138.0, 137.6,36.9, 129.6, 129.2, 128.0, 126.7,126.2, 125.1, 124.7, 120.6, 119.8, 35.0, 33.6,22.4, 16.6, 14.0HRMS(FAB): calcd, for C64H72N2S2 932.5137, found 932.5156

Anal. Calcd. for C64H72 N2S2: C, 82.35; H, 7.77; N, 3.0. Found: C,81.90; H, 7.93; N, 3.55.

Example 43

Preparation ofE,E-1,4-Bis[2′-benzylthio-4′-(N,N-di-p-n-butylphenyl)amino-styryl]benzene(49). To a solution of of 4-(N,N-di-p-n-butylphenyl)amino-2-benzylthiobenzaldehyde (47) (1.80 g, 3.55 mmol) and tetraethylα,α′-p-ylenebisphosphonate (25) (0.66 g, 1.74 mmol) in dry THF (20 ml)at 0° C. was added 5.0 ml of 1 M solution of KOtBu in THF. After 2 hoursthe reaction was quenched by addition of 25 ml of water, then 25 ml ofsaturated brine was added, and the mixture was extracted three timeswith methylene chloride/ether (1:4) (3×60 ml). The combined organiclayer was dried over magnesium sulfate. After removal of solvent, theproduct was purified by flash chromatography using 10% of ethyl acetatein hexanes as eluant and was isolated in 95.4% (1.80 g) yield (including˜10% of E-Z and/or Z-Z isomers by NMR). The products were dissolved intoluene (30 ml), a small iodine crystal was added and the solution wasrefluxed overnight. After removal of solvent, the product was purifiedby flash chromatography using 7% of ethyl acetate in hexanes as eluant.1H NMR (CDCl3, 500 MHz) δppm: 6.8-7.7 (m, 40H), 3.90 (s, 4H, SCH2), 2.58(t, J=8.0 Hz, 8H, CH2), 1.60 (m, 8H, CH2), 1.38 (m, 8H, CH2), 0.94 (t,J=7.0 Hz, 12H, CH₃)¹³C NMR (CDCl₃, 125.7 MHz) δppm: 147.7, 144.8, 137.9,137.4, 136.9, 135.1, 131.5, 129.2, 128.8, 128.4, 127.9, 127.0, 126.8,126.2, 125.7, 125.0, 124.6, 121.339.3, 35.1, 33.7, 22.4, 14.0HRMS (FAB):calcd, for C₇₆H₈₀N₂S₂ 1084.5763, found 1084.5797

Anal. Calcd. for C₇₆H₈₀ N₂S₂: C, 84.08; H, 7.43; N, 2.58. Found: C,84.18; H, 7.66; N, 2.77.

Example 44

Preparation of{5-[bis(4-butylphenyl)amino]-2-[2-(4-{2-[4-[(3-butylphenyl)(4-butylphenyl)amino]-2-(dimethylsulfonio)phenyl]vinyl}phenyl)vinyl]phenyl}(dimethyl)sulfoniumhexafluoroantimonate (52).E,E-1,4-Bis[2′-methylthio-4′-(N,N-di-p-^(n)butylphenyl)aminostyryl]benzene (48) (1.23 g, 1.32 mmol) was dissolved in 30 ml of drymethylene chloride and cooled at −78° C. To this solution was added viasyringe methyl trifluoromethanesulfonate (310 μl, 2.74 mmol) and stirredfor 30 min. while the temperature was maintained at −78° C. Then themixture was stirred for two days at room temperature. The solvent wasremoved under reduced pressure and metathesis of anion was performedwithout isolation of the product.

The residue was dissolved in acetone (30 ml) and 20 ml of NaSbF₆ (0.35g, 1.35 mmol) aqueous solution was added. Upon addition of NaSbF₆, ayellow precipitate was formed immediately. Then the mixture was stirredfor 4 hours and acetone was removed under reduced pressure at roomtemperature. The yellow solid was collected by filtration. The aboveanion-exchange procedure was repeated three times. The yellow solid wascollected, washed four times with water, and then dissolved in smallamount of acetone (˜2 ml). To this solution was added 30 ml of ether anda yellow precipitate was formed immediately. The yellow solid was washedthree times with ether, dried under vacuum and was isolated in 78.7%(1.49 g) yield.¹H NMR (CDCl₃, 500 MHz) δppm: 7.1-8.0 (m, 30H), 3.40 (s,12H, CH₃), 2.64 (t, J=7.5 Hz, 8H, CH₂), 1.62 (m, 8H, CH₂), 1.39 (m, 8H,CH₂), 0.95 (t, J=7.0 Hz, 12H, CH₃)

Anal. Calcd. for C₆₆H₇₈ N₂S₂F₁₂Sb₂: C, 55.24; H, 5.48; N, 1.95. Found:C, 55.77; H, 5.31; N, 2.17.

Example 45

Preparation ofbenzyl{2-{2-[4-(2-{2-[benzyl(methyl)sulfonio]-4-[bis(4-butylphenyl)amino]phenyl}vinyl)phenyl]vinyl}-5-[(3-butylphenyl)(4-butylphenyl)amino]phenyl}methylsulfoniumhexafluoroantimonate (53). E,E-1,4-Bis[2′-benzylthio-4′-(N,N-di-p-n-butylphenyl)amino styryl]benzene (49) (1.47 g, 1.35mmol) was dissolved in 25 ml of dry methylene chloride and cooled at−78° C. To this solution was added via syringe methyltrifluoromethanesulfonate (331 μl, 2.93 mmol). While maintaining thattemperature, the mixture was stirred for 30 min. Then the mixture wasstirred for two days at room temperature. The solvent was removed underreduced pressure and metathesis of anion was performed without isolationof the product. The residue was dissolved in 30 ml of acetone and 20 mlof NaSbF₆ (1.40 g, 5.40 mmol) aqueous solution was added. Then themixture was stirred for 4 hours and acetone was removed under reducedpressure at room temperature. The yellow solid was collected byfiltration. The above anion-exchange procedure was repeated three times.The yellow solid was collected, washed four times with water, and thendissolved in small amount of acetone (˜2 ml). To this solution was added20 ml of ether and a yellow oil was formed. The yellow oil was stirredand cooled at 0° C., and solidified. The yellow solid was washed threetimes with ether, dried under vacuum and was isolated in 74.9% (1.61 g)yield.

Example 46

Preparation of 1,4-n-butoxylbenzene (54) (Wright, M. E.; Mullick, S.;Lackritz, H. S.; Liu, L.-Y. Macromolecules, 1994, 27, 3009). Asuspension of 1,4-hydroquinone (20 g, 0.182 mol) and 1-bromobutane (75g, 0.547 mol) and potassium carbonate (75 g, 0.542 mol) in acetonitrile(400 ml) was heated to reflux for three days. The reaction mixture wasallowed to cool to ambient temperature and poured into water (1000 ml).The precipitates were collected by filtration. The crude product wasrecrystallized twice from ethanol upon cooling at −78° C. to form whiteplate-like crystals in 98.0% (39.6 g) yield.¹H NMR (CDCl₃, 500 MHz)δppm: 6.82 (s, 4H, ArH), 3.91 (t, J=6.7 Hz, 4H, CH₂), 1.75 (m, 4H, CH₂),1.49 (m, 4H, CH₂), 0.98 (t, J=7.2 Hz, 6H, CH₃). ¹³C NMR (CDCl₃, 125.7MHz) δ ppm: 153.1, 115.3, 68.3, 31.4, 19.2, 13.9. GC-MS (relativeintensity %): 222, (M⁺, 43), 166 (Bu-n-Ph-OH⁺, 21.4), 110 (HO-Ph-OH,100).

Example 47

Preparation of 2,5-bis(bromomethyl)-1,4-bis(n-butoxyl)benzene (55). To asuspension of 1,4-bis(n-butoxyl)benzene (7.0 g, 0.0315 mol) andparaformadhyde (1.89 g) in acetic acid (230 ml) was added hydrobromicacid (23 ml) in one portion. The mixture was then heated to 65-70° C.with stirring for 3 h. Cooling to ambient temperature, the mixture waspoured into water (700 ml), the crude product was collected andrecrystallized from methanol and was isolated in 29.3% (3.76 g) yield.¹H NMR (CDCl₃, 500 MHz) δppm: 6.82 (s, 2H, ArH), 4.52 (s, 4H, CH₂), 4.0(t, J=6.2 Hz, 4H, CH₂), 1.80 (m, 4H, CH₂), 1.53 (m, 4H, CH₂), 1.0 (t,J=7.5 Hz, 6H, CH₃)¹³C NMR (CDCl₃, 125.7 MHz) δ ppm: 150.6, 127.4, 114.5,68.6, 31.4, 28.8, 19.3, 13.9GC-MS (relative intensity %): 407, 408, 409(M⁺, 1:2:1).

Example 48

Preparation of 2,5-butoxyl-p-xylene bis(triphenylphosphino)dibromide(56). A solution of 2,5-bis(bromomethyl)-1,4-bis(n-butoxyl)benzene (55)(2.4 g, 5.88 mmol) and triphenylphosphine (4.0 g, 15.25 mmol) in toluene(80 ml) was heated to refluxed for 3 hours. The mixture was cooled toambient temperature, poured into hexane (200 ml) and a white precipitatewas collected. The precipitate was dissolved in methylene chloride (10ml) and reprecipitated in hexane to afford a NMR-pure compound in (4.67g, 85.2%) yield.¹H NMR (CDCl₃, 500 MHz) δppm: 7.5-7.8 (m, 30H, Ar—H),6.72 (s, 2H, ArH), 5.31 (d, J=13.0 Hz, 4H, CH₂), 3.01 (t, J=6.0 Hz, 4H,CH₂), 1.10 (m, 8H, CH₂), 0.79 (t, J=7.0 Hz, 6H, CH₃).

Example 49

Preparation of E,E-1,4-bis(p-methylthiostyryl)-2,5-bis(butoxyl)benzene(59). To a solution of 2,5-butoxyl-p-xylene bis(triphenyl)phosphinobromide (2.0 g, 2.14 mmol) and 4-methylbenzaldehyde (0.64 g, 4.20 mmol)in absolute ethanol (40 ml) was added a solution of sodium ethoxide(8.69 mmol) in 10 ml of absolute ethanol. The reaction mixture wasrefluxed for 15 hours. Upon cooling to ambient temperature 25 ml ofwater was added. The yellow precipitate was collected by filtration andwashed three times with methanol. The isomers were purified by flashchromatography using hexanes/methylene chloride/ethyl acetate (50:40:10)as eluant. The isomers were dissolved in 30 ml of toluene and refluxedwith a small crystal of iodine for 20 hours. The mixture was cooled toambient temperature and brownish crystals were formed. The brownishcrystals were refluxed with activated charcoal in 40 ml of toluene for20 min and the resulting yellow crystals were collected afterhot-filtration in 47.6% (0.53 g) yield.¹H NMR (CDCl₃, 500 MHz) δppm:7.4-7.5 (m, 6H), 7.25 (d, 4H, J=8.5 Hz), 7.11 (s, 2H), 7.09 (d, J=16.0Hz, 2H, ═CH), 4.06 (t, J=6.5 Hz, 4H, CH₂), 2.05 (s, 6H, SCH₃), 1.86 (p,J=6.5 Hz, 4H, CH₂), 1.57 (m, 4H, CH₂), 1.03 (t, J=7.5 Hz, 6H, CH₃)¹³CNMR (CDCl₃, 125.7 MHz) δ ppm: 151.0, 137.5, 134.9, 128.1, 126.9, 126.7,126.6, 122.8, 110.4, 69.1, 31.5, 19.5, 19.4, 15.8, 14.0

Anal. Calcd. for C₃₂H₃₈ O₂S₂: C, 74.09; H, 7.38;. Found: C, 74.12; H,7.42.

Example 50

Preparation of tetraethyl 2,5-bis(butoxyl)-p-xylene phosphonate (58).2,5-bis(bromomethyl)-1,4-bis(n-butoxyl)benzene (55) (2.0 g, 4.90 mmol)and triethyl phosphite (10 ml) was heated to reflux for 24 hours. Afterremoval of unreacted triethyl phosphite under reduced pressure, 10 ml ofhexanes was added to the residue. The mixture was stirred for 10 min andcooled at 0° C.; the solvent was then decanted. The product was washedthree times in this way, dried in vacuo, and isolated in 39.2% (1.2 g)yield. ¹H NMR (CDCl₃, 500 MHz) δppm: 6.91 (s, 2H, ArH), 4.02 (m, 8H,CH₂), 3.93 (t, J=6.0 Hz, 4H, CH₂), 3.22 (d, J=20.0 Hz, 4H, CH₂), 1.75(m, 4H, CH₂), 1.48 (m, 4H, CH₂), 1.24 (t, J=7.0 Hz, 12H, CH₃), 0.97 (t,J=7.2 Hz, 6H, CH₃).

Example 51

Preparation of E,E-1,4-bis(p-methylthiostyryl)-2,5-bis(butoxyl)benzene(59). To a solution of 4-methylthiobenzaldehyde (0.65 g, 4.27 mmol) andtetraethyl 2,5-bis(butoxyl)-p-xylene phosphonate (1.0 g, 1.92 mmol) in30 ml of dry THE was added 1M solution of KO^(t)Bu (5 ml, 5 mmol) at 0°C. The mixture was stirred at 0° C for 3 hours. The reaction wasquenched by addition of water (30 ml). The yellow precipitate wascollected by filtration and washed three times by methanol. The productwas recrystallized from toluene and isolated in 68.1% (0.68 g) yield. ¹HNMR (CDCl₃, 500 MHz) δppm: 7.4-7.5 (m, 6H), 7.25 (d, 4H, J=8.5 Hz), 7.11(s, 2H), 7.09 (d, J=16.0 Hz, 2H, ═CH), 4.06 (t, J=6.5 Hz, 4H, CH₂), 2.05(s, 6H, SCH₃), 1.86 (p, J=6.5 Hz, 4H, CH₂), 1.57 (m, 4H, CH₂), 1.03 (t,J=7.5 Hz, 6H, CH₃)¹³C NMR (CDCl₃, 125.7 MHz) δ ppm: 151.0, 137.5, 134.9,128.1, 126.9, 126.7, 126.6, 122.8, 110.4, 69.1, 31.5, 19.5, 19.4, 15.8,14.0.

Example 52

Preparation ofE,E-{4-[2-(2,5-dibutoxy-4-{2-[4-(dimethylsulfonio)phenyl]vinyl}phenyl)vinyl]phenyl}(dimethyl)sulfoniumtriflate (60). To a solution of E,E-1,4-bis(p-methylthiostyryl)-2,5-bis(butoxyl)benzene (59) (0.68 g, 1.31 mmol) was added methyltrifluorosulfonate (0.44 g, 0.303 ml) at −78° C. The mixture was stirredfor 30 minutes, allowed to rise to ambient temperature and stirredovernight. The mixture was poured into 30 ml of ether; the resultingyellow solid was collected by filtration and was isolated in 1.06 g(95.5%) yield.

¹H NMR (500 MHz, DMSO) δ ppm: 8.06 (d, J=8.5 Hz, 4H), 7.86 (d, J=8.5 Hz,4H), 7.63 (d, J=16.5 Hz, 2H, ═CH), 7.51 (d, J=16.5 Hz, 2H, ═CH), 7.39(s, 2H), 4.12 (t, J=6.2 Hz, 4H, CH₂), 3.27 (s, 12 H, CH₃), 1.82 (m, 4H,CH₂), 1.53 (m, 4H, CH2), 0.99 (t, J=7.0 Hz, 6H, CH₃).

Example 53

Preparation ofE,E-{4-[2-(2,5-dibutoxy-4-{2-[4-(dimethylsulfonio)phenyl]vinyl}phenyl)vinyl]phenyl}(dimethyl)sulfoniumhexafluoroantimonate (61). Sodium hexafluoroantimonate (1.36 g, 5.26mmol) in 20 ml of water was added to a solution ofE,E-{4-[2-(2,5-dibutoxy-4-{2-[4-(dimethylsulfonio)phenyl]vinyl}phenyl)vinyl]phenyl}(dimethyl)sulfoniumtriflate (60) (1.06 g, 1.25 mmol) in 20 ml of acetone. The reactionmixture was stirred for 2 hours. The yellow solid was collected byfiltration and the above procedure was repeated three times, andisolated in 1.14 g (89.4%) yield.

¹H NM (500 MHz, DMSO) δppm: 8.06 (d, J=8.5 Hz, 4H), 7.86 (d, J=8.5 Hz,4H), 7.63 (d, J=16.5 Hz, 2H, ═CH), 7.51 (d, J=16.5 Hz, 2H, ═CH), 7.39(s, 21), 4.12 (t, J=6.2 Hz, 4H, CH₂), 3.27 (s, 12 H, CH₃), 1.82 (m, 4H,CH₂), 1.53 (m, 4H, CH2), 0.99 (t, J=7.0 Hz, 6H, CH₃).

Example 54

Preparation of 4-bromophenyl n-butyl sulfide (62). 4-Bromobenzenethiol(5 g, 26.44 mmol) was added to a solution of sodium methoxide (1.43 g,26.48 mmol) in 20 ml of anhydrous methanol. The mixture was stirred for30 min under nitrogen at room temperature and a solution of methyliodide (4.51 g, 31.77 mmol) in 20 ml anhydrous methanol was then added.The reaction mixture was stirred overnight at room temperature, pouredinto 2 M of NaOH aqueous solution (30 ml) and extracted three times withether (3×100 ml ). The combined organic layer was washed with saturatedsodium chloride solution and dried over anhydrous magnesium sulfate.After removal of solvent, the product was purified by distillation at117-119° C. (0.5 mmHg) and was isolated in 88.4% (5.72 g) yield.

Example 55

Preparation of 4-butylthiobenzaldhyde (63). To a solution of4-bromophenyl n-butyl sulfide (1.5 g, 6.12 mmol) in 60 ml of dry THF wasadded ^(n)BuLi (4.1 ml, 1.6 M in hexanes) at −78° C. under nitrogen. Themixture was stirred for 1 hour at −78° C. and then DMF (2.0 ml) wasadded. The reaction mixture was stirred at room temperature for 2 hours.Then 40 ml of water was added to this mixture, the product was extractedthree times by ether (3×50 ml) and the combined organic layer was driedover magnesium sulfate. After removal of solvent under reduced pressure,the product was purified by flash chromatography column using 10% ofethyl acetate in hexanes as eluant and isolated in 66.7% (0.88 g)yield.¹H NMR (CDCl₃, 500 MHz) δppm: 9.98 (s, 1H, CHO), 7.77 (d, J=8.5Hz, 2H), 7.36 (d, J=8.5 Hz, 2H,), 7.11 (s, 2H), 3.02 (t, J=7.2 Hz, 2H,CH₂), 1.71 (m, 2H, CH₂), 1.50 (m, 2H, CH₂), 0.97 (t, J=7.5 Hz, 6H, CH₃).

Example 56

Preparation of E,E-1,4-bis(p-n-butylthiostyryl)benzene (64). To asolution of 4-n-butylthiobenzaldhyde (0.80 g, 4.12 mmol) and tetraethylp-xylene phosphonate (0.78 g, 2.06 mmol) in 25 ml of dry THF was added a1M solution of KO^(t)Bu (5 ml, 5 mmol) at 0° C. The mixture was stirredat 0° C. for 3 hours. The reaction was quenched by addition of water (30ml). The yellow precipitate was collected by filtration and washed threetimes with methanol. The product was recrystallized from xylene andisolated in 61.5% (0.58 g) yield.

Example 57

Preparation of 1,4-dimethylthiobenzene (65) (Engman, L.; Hellberg, J. S.E. J. Organometallic Chem. 1985, 296, 357). tert-Butyl lithium (25 ml,1.7 M) was added dropwise to a stirred solution of 1,4-dibromobenzene (5g, 0.0212 mol) in 125 ml of THF under nitrogen at −78° C. After 30 minthe temperature was allowed to rise to ambient and sulfur (1.36 g,0.0425 mol) was added while a brisk stream of nitrogen was passedthrough the open system to exclude air. After sulfur was consumed,methyl iodide (6.5 g, 0.0458 mol) in 5 ml of THF was then added and themixture was stirred for another 40 min. The solvent was removed underreduced pressure and 50 ml of water was added to the residue. Themixture was extracted three times with ether (3×100 ml) and the combinedorganic layer was dried over magnesium sulfate. After removal of thesolvent, the product was purified by recrystallization from methanol andwas isolated in 67.7% (2.44 g) yield as a white solid.GC-MS (relativeintensity %): 170 (M⁺, 100), 155 (MeSPh-S⁺, 100).

Example 58

Preparation of 2,5-di(methylthio)-p-xylene (66) (Engman, L.; Hellberg,J. S. E. J. Organometallic Chem. 1985, 296, 357). tert-Butyl lithium(22.5 ml, 1.7 M) was added dropwise to a stirred solution of2,5-dibromo-p-xylene (2.5 g, 9.47 mmol) in 60 ml of THF under nitrogenat −78° C. After 30 min the temperature was allowed to rise to ambientand sulfur (0.61 g, 0.019 mol) was added while a brisk stream ofnitrogen was passed through the open system to exclude air. After sulfurwas consumed, methyl iodide (2.7 g, 0.019 mol) in 2 ml of THF was thenadded and the mixture was stirred for another 40 min. The solvent wasremoved under reduced pressure and 50 ml of water was added to theresidue. The mixture was extracted three times with ether (3×100 ml) andthe combined organic layer was dried over magnesium sulfate. Afterremoval of the solvent, the product was purified by recrystallizationfrom methanol and isolated in 66.7% (1.25 g) yield as a white solid.¹HNMR (CDCl₃, 500 MHz) δppm: 6.98 (s, 2H, Ar—H), 2.44 (s, 6H, CH₃), 2.36(s, 6H, CH₃). ¹³C NMR (CDCl₃, 125.7 MHz) δppm: 134.4, 133.7, 127.1,19.6, 15.9.

Example 59

Preparation 4-n-butoxyl benzaldehyde (71). A suspension of4-hydroxybenzaldehyde (5 g, 0.0409 mol), potassium carbonate (6.91 g,0.05 mol) and 1-bromobutane (6.87 g, 0.05 mol) in 40 ml of acetonitrilewas refluxed for two days. The mixture was allowed to cool to ambienttemperature and 60 ml of water was added. The mixture was extractedthree times with ether (3×120 ml) and the combined organic layer wasdried over magnesium sulfate. After removal of the solvent, the productwas purified by distillation under reduced pressure (0.4 mmHg) at 112°C. and isolated in 86.8% (6.32 g) yield as colorless oil.¹H NMR (CDCl3,500 MHz) δ ppm: 9.84 (s, H, CHO), 7.83 (d, J=9.0 Hz, 2H), 6.99 (d, J=8.5Hz, 2H), 4.05 (t, J=6.5 Hz, 2H), 1.80 (m, 2H), 1.51 (m, 2H), 0.99 (t,J=7.5 Hz, 3H). ¹³C NMR (CDCl3, 125.7 MHz) δ ppm: 134.4, 133.7, 127.1,19.6, 15.9

MS (relative intensity %): 178 (M+, 33), 121 p-CHOPhO+, 100).

Example 60

Preparation of 2,5-dibromo-α,α′-dibromo-p-xylene (67). (Higuchi, H.;Kibayashi, E.; Sakata, Y.; Misumi, S. Tetrahedron 1986, 42, 173).N-bromosuccinimide (13.5 g, 0.075 mol) was added in four portions over 4hours to a refluxing solution of 2,5-dibromo-p-xylene (10 g, 0.0379 mol)containing benzoyl peroxide (0.355 g). The mixture was refluxed for 2hours and then allowed to cool to ambient temperature. After filtration,the solvent was removed under reduced pressure. The resulting yellowishsolid was recrystallized from methanol to afford a 7.58 g (47.4%) yieldof product.1H NMR (CDCl3, 500 MHz) δ ppm: 7.67 (s, 2H, Ar—H), 4.52 (s,2H, CH2)13C NMR (CDCl3, 125.7 MHz) δ ppm: 138.9, 135.3, 123.3, 31.5EIMS(relative intensity %): 422 (M+, 18), 341 (o-Br-m-Br-p-BrCH2PhCH2+,100), 262 (o-Br-m-Br-p-CH2-PhCH2⁺, 91).

Example 61

Preparation of 2-bromo-α,α′-dibromo-p-xylene (68). N-bromosuccinimide(36.54 g, 0.216 mol) was added in five portions over 5 hours to arefluxing solution of 2-bromo-p-xylene (19 g, 0.103 mol) containingbenzoyl peroxide (0.41 g). The mixture was refluxed for 2 hours and thenallowed to cool to ambient temperature. After filtration, the solventwas removed under reduced pressure. The resulting yellowish solid wasrecrystallized from methanol to afford a 14.43 g (41.1%) yield ofproduct.¹H NMR (CDCl₃, 500 MHz) δppm: 7.62 (d, ⁴J=2.0 Hz, 1H), 7.43 (d,³J=8.0 Hz, 1H), 7.33 (dd, ³J=7.7 Hz, ⁴J=1.8 Hz), 4.60 (s, 2H, CH₂),4.41(s, 2H, CH₂)¹³C NMR (CDCl₃, 125.7 MHz) δppm: 139.9, 137.1, 133.7,131.5, 124.5, 32.7, 31.3GC-MS (relative intensity %): 342 (M⁺, 12), 264,263,262 (1:2:1, m-Br-p-BrCH₂-PhCH₂ ⁺, 100), 182, 184 (1:1,m-Br-p-CH2PhCH2⁺, 70).

Example 62

Preparation of tetraethyl 2,5-dibromo-p-xylenebisphosphonate (69). Themixture of 2, 5-dibromo-α,α′-dibromo-p-xylene (67) (7.58 g, 0.018 mol)and triethyl phosphite (60 ml) was refluxed at 180° C. overnight. Theexcess triethyl phosphite was removed under reduced pressure, 60 ml ofhexanes was added, and white solid was formed. The solid was collectedby filtration, washed three times with 20 ml of hexanes and gave 7.93 g(82.2%) of product.¹H NMR (CDCl₃, 500 MHz) δppm: 7.62 (s, 2H, Ar—H),4.06 (m, 8H, CH2), 3.32 (d, J=20.5 Hz, 4H, CH₂), 1.28 (t, J=7.0 Hz, 12H,CH₃)¹³C NMR (CDCl₃, 125.7 MHz) δppm: 135.2, 132.5, 123.6, 62.35, 62.32,33.4, 32.2, 16.31, 16.28GC-MS (relative intensity %): 491 (M⁺, <5%).

Example 63

Preparation of tetraethyl 2-bromo-p-xylenebisphosphonate (70). Themixture of 2-bromo-α,α′-dibromo-p-xylene (68) (14.43 g, 0.042 mol) andtriethyl phosphite (145 ml) was refluxed at 180° C. overnight. Theexcess triethyl phosphite was removed under reduced pressure, 60 ml ofhexanes was added, the mixture was cooled at −78 ° C. and white solidwas formed on vigorous stirring. The solid was collected by rapidfiltration, washed three times with 20 ml of cool hexanes, dried invacuo and isolated in 14.0 g (72.7%) yield as light yellow oil.¹H NMR(CDCl₃, 500 MHz) δppm: 7.51 (s, br, 1H), 7.40 (dd, ³J=7.7 Hz, ⁴J=2.2 Hz,1H), 7.21 (d, ³J=8.0 Hz, 1H) 4.04 (m, 8H, CH2), 3.38 (d, J=21.5 Hz, 2H,CH₂), 3.09 (d, J=21.5 Hz, 2H, CH₂), 1.25 (m, 12H, CH₃).

Example 64

Preparation of 2,5-dibromo-E,E-1,4-bis[p-n-butoxystyryl]benzene (74). Toa solution of p-butoxybenzaldehyde (71) (0.7 g, 3.95 mmol) andtetraethyl 2,5-dibromo-α,α′-p-xylenebisphosphonate (69) (1.02 g, 1.90mmol) in dry THF (25 ml) at 0° C. was added 4 ml of 1 M solution ofKO^(t)Bu in THF. After 2 hours the reaction was quenched by addition of20 ml of methanol. A yellow solid was collected by filtration and washedthree times with methanol to afford NMR-pure product in 0.92 g (82.9%)yield.¹H NMR (CDCl₃, 500 MHz) δppm: 7.83 (s, 2H), 7.48 (d, J=8.5 Hz,4H), 7.22 (d, J=16.5 Hz, 2H, ═CH), 7.01 (d, J=16.0 Hz, 2H, ═CH), 6.91(d, J=9.0 Hz, 4H), 4.0 (t, J=6.5 Hz, 4H, CH2), 1.80 (m, 4H, CH₂), 1.52(m, 4H, CH2), 0.99 (t, J=7.2 Hz, 6H, CH₃)^(—)C NMR (CDCl₃, 125.7 MHz)δppm: 159.5, 137.2, 131.6, 129.9, 129.2, 128.2, 123.4, 122.8, 114.7,67.7, 31.3, 19.2, 13.9.

Example 65

Preparation of 2-bromo-E,E-1,4-bis[p-n-butoxystyryl]benzene (75). To asolution of p-butoxybenzaldehyde (71) (2.0 g, 11.2 mmol) and tetraethyl2-bromo-α,α′-p-xylenebisphosphonate (70) (2.55 g,. 5.5 mmol) in dry THF(70 ml) at 0° C. was added 12 ml of 1 M solution of KO^(t)Bu in THF.After 2 hours the reaction was quenched by addition of 70 ml ofmethanol. A light yellow solid was collected by filtration and washedthree times with methanol to afford NMR-pure product in 2.36 g (84.5%)yield.¹H NMR (CDCl₃, 500 MHz) δppm: 7.70 (s, 1H), 7.62 (d, J=8.5 Hz,1H), 7.47 (d, J=8.0 Hz, 2H), 7.44 (d, J=8.5 Hz, 2H), 7.4 (d, J=7.5 Hz,1H), 7.32 (d, J=16.5 Hz, 1H, ═CH), 7.06 (d, J=16.5 Hz, 1H, ═C), 7.01 (d,J=16.0 Hz, 1H, ═CH), 6.85-6.95 (m, 5H, 4 Ar—H, 1 ═CH), 4.0 (m, 4H, CH2),1.80 (m, 4H, CH₂), 1.52 (m, 4H, CH2), 1.0 (t, J=7.5 Hz, 6H, CH₃)¹³C NMR(CDCl₃, 125.7 MHz) δppm: 159.1, 138.1, 135.7, 130.5, 130.4, 129.7,129.4, 129.2, 128.0, 127.8, 126.2, 125.2, 124.7, 124.5, 124.3, 114.7,67.7, 31.3, 19.2, 13.9.

Example 66

Preparation of 2,5-dimethylthio-E,E-1,4-bis p-n-butoxystyryl]benzene(78). 1.7 M tert-butyl lithium (3.63 ml, 6.17 mmol) was added dropwiseto a stirred solution of2,5-dibromo-1,4-E,E-bis[4-(n-butoxy)styryl]benzene (74) (0.9 g, 1.54mmol) in 20 ml of THF under nitrogen at −78° C. After 30 min thetemperature was allowed to rise to ambient and sulfur (0.10 g, 3.08mmol) was added while a brisk stream of nitrogen was passed through theopen system to exclude air. After sulfur was consumed, methyl iodide(0.46 g, 3.24 mmol) in 0.5 ml of THF was added and the mixture wasstirred for another 1 hour. The solvent was removed under reducedpressure and 20 ml of water was added to the residue. The mixture wasstirred vigorously for 20 min and yellow solid was collected byfiltration. The yellow product was purified by flash columnchromatography using toluene/hexanes from 1:1 to 5:3 as eluant andisolated in 0.39 g (48.7%) yield.

¹H NMR (CDCl₃, 500 MHz) δppm: 7.54 (s, 2H), 7.49 (d, J=9.0 Hz, 4H), 7.42(d, J=16.5 Hz, 2H, ═CH), 7.01 (d, J=16.0 Hz, 2H, ═CH), 6.91 (d, J=9.0Hz, 4H), 4.0 (t, J=6.7 Hz, 4H, CH₂), 2.50 (s, 6H, CH₃), 1.79 (m, 4H,CH₂), 1.52 (m, 4H, CH₂), 0.99 (t, J=7.2 Hz, 6H, CH₃)

¹³C NMR (CDCl₃, 125.7 MHz) δppm: 159.0, 137.0, 136.8, 135.9, 129.7,128.4, 125.1, 123.1, 114.7, 67.7, 31.3, 19.2, 17.3, 13.9

Anal. Calcd. for C₃₂H_(38 O) ₂S₂: C, 74.09; H, 7.38;. Found: C, 73.93;H, 7.43.

Example 67

Preparation of 2-methylthio-E,E-1,4-bis[p-n-butoxystyryl]benzene (79).1.7 M tert-butyl lithium (5.1 ml, 8.67 mmol) was added dropwise to astirred solution of 2-bromo-1,4-E,E-bis[4-(n-butoxy)styryl]benzene (75)(2.3 g, 3.98 mmol) in 50 ml of THF under nitrogen at −78° C. After 30min the mixture was allowed to rise to ambient temperature and sulfur(0.15 g, 4.69 mmol) was added while a brisk stream of nitrogen waspassed through the open system to exclude air. After sulfur wasconsumed, methyl iodide (0.69 g, 4.69 mmol) in 1 ml of THF was added andthe mixture was stirred for 1 hour. The solvent was removed underreduced pressure and 50 ml of water was added to the residue. Themixture was stirred vigorously for 20 min and a light yellow solid wascollected by filtration. The light yellow product was purified by flashcolumn chromatography using toluene/hexanes from 2:3 as eluant andisolated in 1.24 g (66.3%) yield.¹H NMR (CDCl3, 500 MHz) δ ppm: 7.58 (d,J=8.0 Hz, 1H), 7.48 (d, J=8.5 Hz, 2H), 7.45 (d, J=9.0 Hz, 2H), −7.43 (d,J=16.5 Hz, 1H, ═CH), 7.38 (s, 1H), 7.33 (d, J=7.5 Hz, 1H), 7.08 (d,J=16.5 Hz, 1H, ═CH), 7.01 (d, J=16.0 Hz, 1H, ═CH), 6.94 (d, J=16.5 Hz,1H, ═CH), 6.90 (d, J=8.0 Hz, 4H), 4.0 (t, J=6.2 Hz, 4H, CH2), 2.50 (s,3H, CH3), 1.79 (m, 4H, CH2), 1.52 (m, 4H, CH2), 0.99 (t, J=7.2 Hz, 6H,CH3)13C NMR (CDCl3, 125.7 MHz) δ ppm: 158.9, 137.0, 136.8, 135.9, 130.1,129.7, 128.4, 127.9, 127.7, 125.65, 125.59, 123.6, 123.3, 114.7, 67.7,31.3, 19.2, 16.8, 13.8

Anal. Calcd. for C₃₁H₃₆ O₂S: C, 78.77; H, 7.68;. Found: C, 78.52; H,7.65.

Example 68

Preparation of 4,4′-di(n-butyl)triphenylamine (72). To a solution oftris(dibenzylideneacetone)dipalladium (Pd₂(dba)₃) (0.66 g, 0.72 mmol)and bis(diphenylphospino)ferrocene (DPPF) (0.47 g, 0.85 mmol) in 150 mlof dry toluene was added 1-bromo-4-n-butyl benzene (15 g, 70.4 mmol) atroom temperature under nitrogen; the resultant mixture was stirred for10 minutes, and sodium tert-butoxide (10.54 g) and aniline (3.2 g, 34.4mmol) were then added to this solution which was then stirred for 20 hat 90° C. The mixture was allowed to cool, poured into 150 ml of waterand extracted three times (3×200 ml) with ether. The combined organiclayer was dried over anhydrous magnesium sulfate. After removal ofsolvent under reduced pressure, the product was purified by flash columnchromatography using 10% of ethyl acetate in hexanes as eluant and wasisolated in 93.1% (11.6 g) yield.

Example 69

Preparation of 4,4′-dibutyl-4″-formyl triphenylamine (73). To a solutionof 4,4′-di-n-butyldiphenlylamine (72) (11.6 g, 32.3 mmol) in 120 ml ofDMF at 0° C. was added POCl₃ (6.93 g, 45.2 mmol) dropwise. The resultingmixture was stirred at 95-100° C. under nitrogen for 20 hour. Themixture was cooled, poured into 300 ml of ice-water slowly, neutralizedwith 4 M aqueous NaOH and extracted three times (3×200 ml) with ether.The combined organic layer was washed with saturated brine and driedover magnesium sulfate. After removal of solvent, the product waspurified by flash chromatography using 10% of ethyl acetate in hexanesas eluant and was isolated in 72.3% (8.66 g) yield. ¹H NMR (CDCl₃, 500MHz) δppm: 9.79 (s, 1H, CHO), 7.64 (d, J=9.0 Hz, 2H), 7.15 (d, J=8.5 Hz,4H), 7.09 (d, J=8.5 Hz, 4H), 6.95 (d, J=9.0 Hz, 2H), 2.61 (d, J=7.7 Hz,4H, CH₂), 1.62 (m, 4H, CH₂), 1.38 (m, 4H, CH₂), 0.95 (t, J=7.2 Hz, 6H,CH₃).

Example 70

Preparation of 2,5-dibromo-E,E-1,4-bis[N,N,N′,N′-tetra-(4-n-butylphenyl)aminostyryl]benzene (76). To a solution of 4,4′-dibutyl-4″-formyltriphenylamine (73) (3.1 g, 8.36 mmol) and tetraethyl2,5-dibromo-α,α′-p-xylenebisphosphonate (69) (2.17 g, 4.05 mmol) in dryTHF (50 ml) at 0° C. was added 9 ml of a 1 M solution of KO^(t)Bu inTHF. After 2 hours the reaction was quenched by addition of 10 ml ofwater; THF was removed under reduced pressure. 50 ml of water was addedto the residue, the mixture was extracted three times by methylenechloride/ether (1:4) (3×120 ml). The combined organic layer was driedover magnesium sulfate. After removal of solvent, the product waspurified by flash chromatography using toluene/hexanes (1/4) as eluantand was isolated in 83.2% (3.37 g) yield.¹H NMR (CDCl₃, 500 MHz) δppm:7.82 (s, 2H), 7.37 (d, J=8.5 Hz, 4H), 7.20 (d, J=16.0 Hz, 2H, ═CH), 7.08(d, J=8.0 Hz, 8H), 7.03 (d, J 8.0 Hz, 8H), 7.0 (d, J=8.5 Hz, 4H),6.97(d, J=16.0 Hz, 2H, ═CH), 2.57 (t, J=7.7 Hz, 8H, CH₂), 1.60 (m, 8H,CH₂), 1.37 (m, 8H, CH2), 0.94 (t, J=7.5 Hz, 12H, CH₃)¹³C NMR (CDCl₃,125.7 MHz) δppm: 148.5, 144.9, 138.1, 137.1, 131.5, 129.8, 129.5, 129.2,127.7, 124.9, 123.3, 122.9, 121.8, 35.1, 33.7, 22.4. 14.0.

Example 71

Preparation of 2-bromo-E,E-1,4-bis[N,N,N′N′-tetra-(4-n-butylphenyl)aminostyryl]benzene (77). To a solution of 4,4′-dibutyl-4″-formyltriphenylamine (73) (4.0 g, 10.8 mmol) and tetraethyl2-bromo-α,α′-p-xylenebisphosphonate (70) (2.46 g, 5.37 mmol) in dry THF(65 ml) at 0° C. was added 11 ml of 1 M solution of KO^(t)Bu in THF.After 2 hours the reaction was quenched by addition of 10 ml of waterand THF was removed under reduced pressure. 50 ml of water was thenadded to the residue and the mixture was extracted three times withmethylene chloride/ether (1:4) (3×120 ml). The combined organic layerwas dried over magnesium sulfate. After removal of solvent, the productwas purified by flash chromatography using methylene chloride/ethylacetate/hexanes (1/1/4) as eluant and was isolated in 86.2% (4.27 g)yield.¹H NMR (CDCl₃, 500 MHz) δppm: 7.68 (s, 1H), 7.62 (d, J=8.5 Hz,1H), 7.28-7.42 (m, 6H), 6.96-7.12 (m, 22H), 6.85 (d, J=16.0 Hz, 1H,═CH), 2.57 (d, J=7.7, 8H, CH₂), 1.58 (m, 8H, CH₂), 1.37 (m, 8H, CH₂),0.94 (t, J=7.2 Hz, 12H, CH₃)¹³C NMR (CDCl₃, 125.7 MHz) δppm: 148.2,148.1, 145.0, 138.1, 137.9, 135.7, 130.5, 130.4, 130.1, 129.9, 129.2,127.5, 127.3, 126.1, 125.2, 124.7, 124.4, 124.2 122.2, 122.1, 35.1,33.7, 22.4, 14.0.

Example 72

Preparation of 2,5-dimethythio-E,E-1,4-bis[N,N,N′,N′-tetra-(4-n-butylphenyl)aminostyryl]benzene (80). 1.7 M tert-butyl lithium (3.7 ml, 6.29mmol) was added dropwise to a stirred solution of2,5-dibromo-E,E-1,4-bis[N,N,N′,N′-tetra-(4-n-butylphenyl)aminostyryl]benzene (76) (1.5 g, 1.50 mmol) in 20 ml of THF undernitrogen at −78° C. After 30 min the mixture was allowed to rise toambient temperature and sulfur (0.10 g, 3.12 mmol) was added while abrisk stream of nitrogen was passed through the open system to excludeair. After sulfur was consumed, methyl iodide (0.44 g, 3.12 mmol) in 1ml of THF was then added and the mixture was stirred for 1 hour. Thesolvent was removed under reduced pressure and 30 ml of water was addedto the residue. The mixture was extracted three times with ether (3×100ml) and the combined organic layer was dried over magnesium sulfate.After removal of solvent, the residue was washed three times withmethanol to remove a side product. The product was purified three timesby flash column chromatography using toluene/hexanes in ratios varyingfrom 1:4 to 3:7 as eluent to afford a poor yield of the product. ¹H NMR(CDCl₃, 500 MHz) δppm: 7.53 (s, 2H), 7.42 (d, J=16.0 Hz, 2H, ═CH), 7.39(d, J=8.0 Hz, 4H), 7.07 (d, J=8.5 Hz, 8H), 7.03 (d, J=8.0 Hz, 8H),6.96-7.02 (m, 5H, 4 Ar—H, 1 ═CH), 2.57 (t, J=7.7 Hz, 8H, CH2), 2.48 (s,6H, SCH₃), 1.60 (m, 8H, CH₂), 1.37 (m, 8H, CH₂), 0.94 (t, J=7.2 Hz, 12H,CH₃)¹³C NMR (CDCl₃, 125.7 MHz) δppm: 148.0, 145.0, 137.8, 136.7, 134.2,130.4, 130.0, 129.2, 127.5, 125.3, 124.7, 123.1, 122.2, 35.0, 33.7,22.4. 17.3, 14.0.

Example 73

Preparation of 2-methylthio-E,E-1,4-bis[N,N,N′,N′-tetra-(4-n-butylphenyl)aminostyryl]benzene (81). 1.7 M tert-butyl lithium (5.1 ml, 8.67mmol) was added dropwise to a stirred solution of2-bromo-E,E-1,4-bis[N,N,N′,N′-tetra-(4-n-butylphenyl)aminostyryl]benzene (77) (2.0 g, 2.17 mmol) in 50 ml of THF undernitrogen at −78° C. After 30 min the mixture was allowed to rise toambient temperature and sulfur (0.076 g, 2.38 mmol) was added while abrisk stream of nitrogen was passed through the open system to excludeair. After sulfur was consumed, methyl iodide (0.34 g, 2.39 mmol) in 1ml of THF was added and the mixture was stirred for 1 hour. The solventwas removed under reduced pressure and 50 ml of water was added to theresidue. The mixture was extracted three times with ether (3×100 ml) andthe combined organic layer was dried over magnesium sulfate. Afterremoval of solvent, the residue was washed three times with methanol toremove a side product. The yellow product was purified by flash columnchromatography using toluene/hexanes in ratios varying from 1:4 to 3:7as eluant and isolated in 0.62 g (32.1%) yield.¹H NMR (CDCl₃, 500 MHz)δppm: 7.57 (d, J=8.0 Hz, 1H), 7.44 (d, J=16.0 Hz, 1H, ═CH), 7.39 (d,J=8.5 Hz, 2H), 7.38 (s, 1H), 7.35 (d, J=8.5 Hz, 2H), 7.32 (d, J=8.5 Hz,1H), 6.7-7.1 (m, 22H), 6.93 (d, J=16.0 Hz, 1H, ═CH), 2.57 (d, J=7.7, 8H,CH₂), 2.50 (s, 3H, CH₃), 1.60 (m, 8H, CH₂), 1.37 (m, 8H, CH₂), 0.94 (t,J=7.2 Hz, 12H, CH₃)¹³C NMR (CDCl₃, 125.7 MHz) δ ppm: 147.9, 145.1,137.82, 137.76, 137.1, 136.8, 135.9, 130.7, 130.3, 129.7, 129.1, 128.4,127.4, 127.2, 125.6, 124.65, 124.60, 123.6, 123.3, 122.4, 122.3, 35.0,33.7, 22.4, 16.8, 14.0 Anal. Calcd. for C₆₃H₇₀ N₂S: C, 85.28; H, 7.95;.N, 3.16. Found: C, 85.46; H, 8.04; N, 3.23.

Example 74

Preparation ofE,E{2,5-bis[2-(4-butoxyphenyl)vinyl]phenyl}(dimethyl)sulfonium triflate(82).2-Methylthio-E,E-1,4-bis[N,N,N′,N′-tetra-(4-n-butylphenyl)aminostyryl]benzene(0.39 g, 0.75 mmols) was dissolved in dry methylene chloride (14 ml).The solution was cooled to −78° C. and placed under a nitrogenatmosphere. Methyl trifluoromethanesulfonate (0.21 ml, 1.88 mmol) wasadded via syringe to the cooled solution in the dark. After mixing for30 minutes at −78° C. the solution was stirred at room temperature fortwo days. 50 ml of ether was added to the mixture and the resultingsolid was collected by filtration and washed three times with ether togive the light yellow product in 0.56 g (85%) yield.¹H NMR (CDCl₃, 500Mz) δ ppm: 7.54 (d, J=8.5 Hz, 2H), 7.42 (d, J=16, 2H), 7.18 (d, J=16.0Hz, 2H), 7.00 (t, J=9.0 Hz, 8H), 4.00 (m, 4H, CH₂), 3.32 (s, 12H, CH₃),1.70 (m, 4H, CH₂), 1.43 (m, 4H, CH₂), 0.94 (m, 6H, CH₃).

Example 75

Preparation of 10-(4-butylphenyl)-10H-phenothiazine (83). To a solutionof tris(dibenzylideneacetone)dipalladium (Pd₂(dba)₃) (0.30 g, 0.33 mmol)and bis(diphenylphosphino)ferrocene (DPPF) (0.22 g, 0.40 mmol) in drytoluene (60 ml) under nitrogen atmosphere was added4-(butyl)phenylbromide (3.21 g, 15.1 mmol) at room temperature, and theresultant mixture was stirred for 10 min., sodium tert-butoxide (4.0 g)and phenothiazine (3.0 g, 15.1 mmol) were added to this solution andstirred at 90° C. overnight under nitrogen. The reaction mixture waspoured into water (80 ml), extracted three times with ether (100 ml×3)and dried over anhydrous magnesium sulfate. The product was purified byflash column chromatography using 5% ethyl acetate in hexane as eluantand was isolated in 81% (4.03 g) yield as a pale yellow solid.¹H NMR(CDCl₃, 500 MHz) δppm: 7.41 (d, J=7.0 Hz, 2H), 7.29 (d, J=8.0 Hz, 2H),7.0 (dd, J=7.5 Hz, J=1.5 Hz, 2H), 6.7-6.9 (m, 4H), 6.20 (d, J=7.5 Hz,2H), 2.72 (t, J=7.5 Hz, 2H, CH₂), 1.7 (m, 2H, CH₂), 1.44 (m, 2H, CH₂),0.99 (t, J=7.0 Hz, 3H, CH₃).

Example 76

Preparation of 10-(4-butylphenyl)-5-phenyl-10H-phenothiazin-5-iumhexa-fluorophosphate (84). A mixture of10-(4-butylphenyl)-10H-phenothiazine (83) (1.44 g, 4.34 mmol),diphenyliodonium hexafluorophosphate (1.85 g, 4.34 mmol) and copper (I)benzoate (0.10 g) was heated at 120° C. for 3 hours under nitrogen. Uponcooling to ambient temperature, the mixture was transferred to amortar-and-pestle and 50 ml of ether was added. The solid was finelypowdered, washed with ether, collected by filtration and washed threetimes with ether. Without further purification, it was isolated in 98.2%(2.36 g) yield as a pale yellow solid.

¹H NMR (DMSO, 500 MHz) δppm: 8.37 (d, J=8.0 Hz, 2H1), 7.6-7.8 (m, 5H),7.4-7.5 (m, 4H), 7.20 (d, J=7.5 Hz, 2H), 6.74 (d, J=8.5 Hz, 2H), 2.73(t, J=8.0 Hz, 2H, CH₂), 1.65 (m, 2H, CH₂), 1.38 (m, 2H, CH₂), 0.94 (t,J=7.0 Hz, 3H, CH₃).

Example 77

Preparation ofN,N-bis(4butylphenyl)-N-(4-{2[4-(10H-phenothiazin-10-yl)phenyl]vinyl}phenyl)amine(86). To a solution of tris(dibenzylideneacetone) dipalladium(Pd₂(dba)₃) (0.13 g, 0.14 mmol) and bis(diphenylphosphino)ferrocene(DPPF) (0.10 g, 0.17 mmol) in dry toluene (20 ml) under nitrogenatmosphere was added 4-[2-(4-bromophenyl)vinyl]-N,N-bis(4-butylphenyl)aniline (2.60 g, 4.83 mmol) at room temperature, andthe resultant mixture was stirred for 10 min. Sodium tert-butoxide (1.3g) and phenothiazine (0.96 g, 4.83 mmol) were then added to thissolution, which was then stirred at 90° C. overnight under nitrogen. Thereaction mixture was poured into water (60 ml), extracted three timeswith ether (100 ml×3) and dried over anhydrous magnesium sulfate. Theproduct was purified by flash column chromatography using 2% ethylacetate in hexane as eluant and was isolated in 60% (1.91 g) yield as ayellow solid.

¹H NMR (CDCl₃, 500 MHz) δppm: 7.70 (d, J=8.5 Hz, 2H), 7.39 (d, J=7.0 Hz,2H), 7.35 (d, J=8.5 Hz, 2H), 7.13 (d, J=16.0 Hz, 1H, ═CH), 7.09 (d.J=8.5 Hz, 4H), 7.0-7.03 (m, 9H), 6.87 (td, J=7.5 Hz, J=1.5 Hz, 2H), 6.82(td, J=7.5 Hz, J=1.5 Hz, 2H, 2H), 6.29 (dd, J=8.5 Hz, J=1.5 Hz, 2H),2.59 (t, J=7.5 Hz, 4H, CH₂), 1.63 (m, 4H, CH₂), 1.40 (m, 4H, CH₂), 0.96(t, J=7.0 Hz, 6H, CH₃). ¹³C NMR (CDCl₃, 125 MHz) δppm: 148, 145, 144,140, 137.9, 137.6, 131, 130, 129.5, 129.2, 128, 127, 126.8, 126.7, 125,124.7, 122.5, 122.2, 120, 116, 35, 34, 22, 14. HR-FAB: calcd. forC₄₆H₄₄N₂S: M⁺, 656.32; found M⁺, 656.3233.

Example 78

Preparation of10-(2-{4-[bis(4-butylphenyl)amino]phenyl}vinyl)-5-phenyl-10H-phenothiazin-5-iumhexafluorophosphate (87). A mixture ofN,N-bis(4-butylphenyl)-N-(4-{2-[4-(10H-phenothiazin-10-yl)phenyl]vinyl}phenyl)amine(0.5 g, 0.76 mmol), diphenyliodonium hexafluorophosphate (0.32 g, 0.76mmol) and copper (I) benzoate (0.02 g) in 10 ml of chlorobenzene washeated at 120° C. for 3 hours under nitrogen. Upon cooling to ambienttemperature, the mixture was poured into 50 ml of hexanes. The yellowprecipitate was collected by filtration and washed three times withether. The product was purified by flash column using methylene chlorideas eluant to give 0.13 g of lightly yellow product.

¹H NMR (d₆-DMSO, 500 MHz) δppm: 8.12 (d, J=8.0 Hz, 2H), 7.82 (d, J=8.0Hz, 2H), 7.54-7.74 (m, 5H), 7.40-7.52 (m, 4H), 7.34 (d, J=8.0 Hz, 2H),7.28 (d, J=16 Hz, 4H), 7.1-7.23 (m, 8H), 6.80-7.04 (m, 8H), 2.58 (t,J=7.5 Hz, 4H, CH₂), 1.63 (m, 4H, CH₂), 1.40 (m, 4H, CH₂), 0.96 (t, J=7.0Hz, 6H, CH₃).

Example 79

Preparation of 3-bromophenyldiazonium hexafluorophosphate (88). To asolution of hydrochloric acid (36.5%, 24 ml) in 180 ml of water wasadded m-bromoaniline in one portion (15 g, 0.087 mol). Then a solutionof sodium nitrite (7.5 g) in 18 ml of water was added slowly while themixture was maintained between −5° C. and 10° C. The mixture was stirredfor an additional 30 min and the precipitate was collected byfiltration. The solid was dissolved in 20 ml of methanol and then pouredinto 300 ml of ether; the white solid was collected by filtration toafford 6.1 g (63%) of 3-bromophenyldiazonium hexafluorophosphonate.

Example 80

Preparation of 3-bromo diphenylsulfide (89). To a solution of3-bromophenyldiazonium hexafluorophosphonate (88) (2.5 g, 7.59 mmol) in15 ml of anhydrous DMSO was added a solution of benzenethiolate 91.0 g,7.57 mmol) in 30 ml of DMSO at 0° C. The mixture was stirred at roomtemperature for 24 hours, poured into 100 ml of water and then extractedthree times with ether. The combined organic layer was dried overanhydrous magnesium sulfate. After removal of solvent, the product waspurified by flash chromatography using hexane as eluant.

¹H NMR (CDCl₃, 500 MHz) δ ppm: 7.38-7.43 (m, 3H), 7.28-7.38 (m, 4H),7.20 (dt, J=8.0 Hz, J=1.5 Hz, 1H), 7.14 (t, J=7.5 Hz, 1H).

¹³C NMR (CDCl₃, 125 MH) δ ppm: 139.0, 133.8, 132.3, 132.2, 130.3, 129.6,129.4, 128.3, 127.9, 122.9.

Example 81

Preparation of 3-phenylthio triphenylamine (90). To a solution oftris(dibenzylideneacetone)dipalladium (Pd₂(dba)₃) (0.05 g, 0.05 mmol)and bis(diphenylphosphino)ferrocene (DPPF) (0.04 g, 0.07 mmol) in drytoluene (10 ml) under nitrogen atmosphere was added3-bromodiphenylsulfide (89) (0.75 g, 2.83 mmol) at room temperature, andthe resultant mixture was stirred for 10 min. Sodium tert-butoxide (0.75g) and diphenylamine (0.48 g, 2.83 mmol) were added to this solution andstirred at 90° C. overnight under nitrogen. The reaction mixture waspoured into water (60 ml), extracted three times with ether (60 ml×3)and dried over anhydrous magnesium sulfate. The product was purified byflash column chromatography using hexane as eluant and was isolated in60% (0.6 g) of yellow solid.

Example 82

Preparation of [3-(diphenylamino)phenyl](diphenyl)sulfonium (91). Themixture of 3-phenylthio triphenylamine (90) (0.6 g, 1.70 mmol) anddiphenyliodonium hexafluorophosphate (0.73 g, 1.70 mmol) and copper (I)benzoate (0.02 g) in 10 ml of chlorobenzene was heated at 120° C. for 3hours under nitrogen. Upon cooling to ambient temperature, the mixturewas poured into 50 ml of hexanes. The yellow precipitate was collectedby filtration and washed three times with ether. The product waspurified by flash column using methylene chloride as eluant to give 0.26g of a light yellow product.

¹H NMR (CDCl₃, 500 MHz) δppm: 7.74 (t, J=7.0 Hz, 2H), 7.67 (t, J=7.0 Hz,4H), 7.61 (d, br, J=8.0 Hz, 4H), 7.40 (t, J=8.0 Hz, 1H), 7.26-7.34 (m,5H), 7.14 (t, J=7.0 Hz, 1H), 7.08 (d, br, J=7.5 Hz, 4H), 7.03 (dd, J=8.0Hz, J=2.0 Hz, 1H), 6.84 (t, J=2.0 Hz, 1H).

Example 83

Preparation of 4-N,N-dibutylaminobenzaldehyde (92). A solution ofdibutylaniline (20 g, 0.0975 mol) in 12 ml of dichloroethane was addedto a solution of DMF (25 ml) and POCl₃ (10 ml) in 12 ml ofdichloroethane at 0° C. The mixture was heated to reflux for 3 hourswith vigorous evolution of HCl and was allowed to cool to ambienttemperature. 300 ml of methylene chloride was added, washed with a 2Msolution of sodium hydroxide and three times with water, and dried overanhydrous sodium sulfate. After removal of solvent, the product waspurified by flash chromatography using ethyl acetate and hexanes (1:10)as eluant and was isolated in 18.15 g (79.9%).

¹H NMR (CDCl₃, 500 MHz) δppm: 9.72 (s, 1H, CHO), 7.70 (d, J=8.5 Hz, 2H),6.65 (d, J=8.5 Hz, 2H), 3.35 (t, J=7.5 Hz, 4H, CH₂), 1.61 (m, 4H, CH₂),1.38 (m, 4H, CH₂), 0.98 (t, J=7.5 Hz, 6H, CH₃)

¹³C NMR (CDCl₃, 125.7 MHz) δ ppm: 189.9, 152.5, 132.2, 124. 4, 112.7,110.6, 50.8, 29.2, 20.2, 13.9.

Example 84

Preparation of 4-N,N-dimethylaminobenzylalcohol (93). NaBH₄ (0.976 g,0.025 mol) was added to a solution of 4-N,N-dibutylaminobenzaldehyde(92) (2 g, 0.012 mol) in 100 ml of methanol at room temperature. Theresultant mixture was stirred for 30 min and poured into 100 ml ofwater. The mixture was extracted three times with ether and combinedorganic layer was washed with brine and dried over magnesium sulfate.Removal of solvent was isolated in 2.71 g (89.4%) yield as an NMR-purecompound.

¹H NMR (CDCl₃, 500 MHz) δ ppm: 7.21 (d, J=8.0 Hz, 2H), 6.63 (d, J=8.5Hz, 2H), 4.55 (d, J=5.5 Hz, 2H, CH₂O), 3.27 (t, J=7.7 Hz, 4H, CH₂), 1.57(m, 4H, CH₂), 1.36 (m, 4H, CH₂), 0.96 (t, J=7.5 Hz, 6H, CH₃)

¹³C NMR (CDCl₃, 125.7 MHz) δppm: 147.9, 128.9, 127,2, 111.5, 65.5, 50.8,29.3, 20.3, 14.0.

Example 85

Preparation of 4-N,N-dibutylaminobenzyl chloride hydrochloride (94).4-(dibutylamino)benzylalcohol (93) (4.32 g) and concentratedhydrochloric acid (40 ml) were heated at 110° C. for 15 h. The volatilematerial was removed on a rotary evaporator to give the product in 96.1%(5.14 g) yield.¹H NMR (CDCl₃, 500 MHz) dppm: 7.76 (d, J=8.0 Hz, 2H),7.55 (d, J=8.0 Hz, 2H), 4.60 (s, 2H, CH₂), 3.20 (d, br, 4H, CH₂, 1.90(d, br, 4H, CH₂), 1.36 (d, br, 4H, CH₂), 0.85 (t, J=6.2 Hz, 6H, CH₃).

Example 86

Preparation of diethyl 4-dibutylaminobenzyl phosphonate (95). A solutionof 4-N,N-dibutylaminobenzyl chloride hydrochloride (94) (6.34 g, 21.8mmol) and triethyl phosphite (100 ml) was heated to reflux for 24 hours.Excess triethyl phosphite was removed under reduced pressure, thereminder was neutralized with saturated NaHCO₃ solution and extractedthree times with ether. The combined organic layer was dried overmagnesium sulfate. Removal of solvent was isolated in 6.97 g (90.1% )yield as NMR-pure compound. ¹H NMR (CDCl₃, 500 MHz) δ ppm: 7.10 (dd,³J=9.0 Hz, ⁴J=2.5 Hz, 2H), 6.57 (d, J=8.5 Hz, 2H), 4.01 (m, 4H, PCH₂),3.23 (t, J=7.5 Hz, 4H, NCH₂), 3.05 (d, J=21 Hz, 2H, CH₂), 1.54 (m, 4H,CH₂), 1.36 (m, 4H, CH₂), 1.25 (t, J=7.5 Hz, 6H, CH₃), 0.95 (t, J=7.0 Hz,6H, CH₃).

Example 87

Preparation of 4-N-tert-butoxycarbonyl-N′-(p-formylphenyl)piperazine(piperazinobenzaldehyde (97). To a mixture of piperazine (10.41 g, 0.121mol) and K₂CO₃ (5.67 g, 0.041 mol) in 15 ml of DMSO was added dropwise4-fluorobenzaldehyde (5 g, 0.0403 mol) in 5 ml of DMSO at 100° C. Theresultant mixture was stirred at 100° C. overnight. The mixture wasallowed to cool to ambient temperature and poured into 500 ml of waterto remove excess piperazine. The yellow solid was collected byfiltration and washed three times by water. The product was used in thenext step without further purification.

To a solution of 4-piperazinobenzaldehyde (4.83 g, 0.0254 mol) anddi-tert-butyl dicarbonate (5.55 g, 0.0254 mol) in 60 ml of methylenechloride was added triethylamine (2.52 g, 0.0254 mol) at 0° C. Themixture was stirred at 0° C. for 2 hours, washed three times with waterand dried over anhydrous sodium sulfate. The product was purified byflash chromatography using ethyl acetate/hexanes varying in ratio from1/4 to 3/7 and was isolated in a yield (over two steps) of 47.5% (5.56g)¹H NMR (500 MHz, CDCl₃) δ ppm: 9.80 (s, 1H, CHO), 7.77 (d, J=8.5 Hz,2H), 6.91 (d, J=8.5 Hz, 2H), 3.59 (m, 4H, CH₂), 3.39 (m, 4H, CH₂), 1.49(s, 9H, CH₃)¹³C NMR (125.7 MHz, CDCl₃) δppm: 190.4, 154.8, 154.6, 131.8,127.4, 113.7, 80.2, 47.0, 28.4.

Example 88

Preparation of 4-N,N-di-n-butylamino-4′-N′-t-butoxycarbonylpiperazinostilbene (98). To a solution of diethyl4-N,N-di-n-butylaminobenzylphosphonate (95) (2.0 g, 5.63 mmol) and4-N-tert-butoxycarbonylpiperazinobenzaldehyde (97) (1.63 g, 5.63 mmol)in 30 ml of THF was added 1M potassium tert-butoxide (6 ml) in THF at 0°C. The mixture was stirred for 2 h at 0° C. and allowed to rise toambient temperature. The reaction was quenched by addition of 40 ml ofwater. The mixture was extracted three times with 70 ml of ether and thecombined organic layer was dried over anhydrous magnesium sulfate. Afterremoval of solvent, the product was purified by recrystallization frommethanol to give a yield of 2.05 g (74.2%).¹H NMR (CDCl₃, 500 MHz) δppm:7.39 (d, J=8.5 Hz, 2H), 7.34 (d, J=9.0 Hz, 2H), 6.85-6.95 (m, overlap,3H), 6.81 (d, J=16.5 Hz, 1H, ═CH), 6.61 (d, J=9.0 Hz, 2H), 3.59 (t,J=4.7 Hz, 4H, CH₂), 3.28 (t, J=7.2 Hz, 4H, CH₂), 3.15 (s, br, 4H, CH₂),1.58 (m, 4H, CH₂), 1.49 (s, 9H, CH₃), 1.37 (m, 4H, CH₂), 0.96 (t, J=7.2Hz, 6H, CH₃).¹³C NMR (CDCl₃, 125.7 MHz) δppm: 154.7, 149.9, 147.4,138.6, 127.4, 126.8, 126.6, 124.8, 123.2, 116.6, 111.6, 79.9, 50.8,49.3, 29.4, 28.4, 20.3, 14.0 (one carbon was not observed).

HRMS (FAB): calcd for C₃₁H₄₅N₃O₂: M⁺491.35. Found 491.3519.

Anal. Calcd. for C₃₁H₄₅N₃O₂: C, 75.72; H, 9.22;. N, 8.55. Found: C,75.76; H, 9.31; N, 8.65.

Example 89

Preparation of 4-N,N-di-n-butylamino-4′-piperazino stilbene (99). To asolution of 4-N,N-di-n-butylamino-4′-N′-tert-butoxycarbonylpiperazinostilbene (98) (0.5 g, 1.02 mmol) in 20 ml of THF was added 2 ml of 2Mhydrochloric acid. The mixture was heated to reflux for 4 h and allowedto cool to room temperature. The solution was neutralized with asolution of sodium hydroxide and extracted three times with ether (30ml). The combined organic layer was dried over anhydrous magnesiumsulfate. After removal of solvent, the product was purified byrecrystallization from methanol to give a yield of 0.36 g (89.7%).¹H NMR(CDCl₃, 500 MHz) δppm: 7.39 (d, J=9.0 Hz, 2H), 7.34 (d, J=9.0 Hz, 2H),6.85-6.95 (m, overlap, 3H), 6.82 (d, J=16.0 Hz, 1H, ═CH), 6.61 (d, J=8.5Hz, 2H), 3.28 (t, J=7.7 Hz, 4H, CH₂), 3.16 (t, J=4.7 Hz, 4H, CH₂), 3.04(t, J=4.7 Hz, 4H, CH₂), 1.58 (m, 4H, CH₂), 1.36 (m, 4H, CH₂), 0.96 (t,J=7.2 Hz, 6H, CH₃). ¹³C NMR (CDCl₃, 125.7 MHz) δppm: 150.5, 147.4,130.0, 127.3, 126.7, 126.2, 125.0, 123.4, 116.1, 111.6, 50.8, 50.3,46.1, 29.4, 20.3, 14.0

HRMS (FAB): calcd for C₂₆H₃₇N₃: M⁺391.30. Found 491.2992.

Anal. Calcd. for C₂₆H₃₇N₃: C, 79.75; H, 9.52;. N, 10.73. Found: C,78.92; H, 9.31; N, 10.72.

Example 90

Preparation of 4-N,N-di-n-butylamino-4′-(1-piperazino)stilbeneN′-triphenyl sulfonium hexafluorophosphate (100). The mixture of4-N,N-di-n-butylamino-4′-(1-piperazino)stilbene (99) (0.80 g, 2.04 mmol)and 4-fluorotriphenylsulfonium hexafluorophosphate (TPSP) in 10 ml ofN,N-dimethyl sulfoxide was heated to 100° C. for 6 hours. Upon coolingto ambient temperature, the mixture was poured into a 5% aqueoussolution of potassium hexafluorophosphate. The yellow solid wascollected by filtration and washed three times with the above solution.The product was purified by flash chromatography using neutral aluminaand methylene chloride/methanol as eluant.

¹H NMR (CDCl₃, 500 MHz) δ ppm: 7.69 (t, br, J=7.5 Hz, 2H), 7.62 (t,J=7.5 Hz, 4H), 7.54 (d, J=7.5 Hz, 4H), 7.52 (d, J=9.5 Hz, 2H), 7.35 (d,J=8.5 Hz, 2H), 7.33 (d, J=9.0 Hz, 2H), 7.07 (d, J=9.0 Hz, 2H), 6.87 (d,J=16.0 Hz, 1H, ═CH), 6.85 (d, J=8.5 Hz, 2H), 6.78 (d, J=16.0 Hz, 1H,═CH), 6.61 (d, J=8.5 Hz, 2H), 3.28 (t, J=7.7 Hz, 4H, CH₂), 3.30 (t, br,4H, CH₂), 3.04-3.3 (m, 8H), 1.56 (m, 4H, CH₂), 1.34 (m, 4H, CH₂), 0.96(t, J=7.0 Hz, 6H, CH₃).¹³C NMR (CDCl₃, 125.7 MHz) δppm: 154.6, 149.1,147.5, 134.1, 133.3, 131.5, 130.6, 130.1, 127.4, 126.8, 126.6, 126.0,124.8, 123.2, 116.2, 115.7, 111.6, 105.7, 50.8, 48.6, 46.4, 29.4, 20.4,14.0

HRMS (FAB): calcd. for C₄₄H₅₀N₃S: M⁺652.37. Found 652.3721.

Anal. Calcd. for C₄₄H₅₀N₃F₆PS: C, 67.23; H, 6.32;. N, 5.27. Found: C,67.47; H, 6.61; N, 5.22.

Example 91

Preparation of 2,5-bis-(chloromethyl)-1,4-dimethoxybenzene (101). To astirred solution of the dimethyl ether of hydroquinone (10.3 g, 74.5mmol), 60 ml of dioxane and 10 ml concentrated hydrochloric acid wasadded two portions of 37% formalin (11 ml) at thirty-minute intervals.During the period of addition, hydrogen chloride gas was passed through.Stirring and the introduction of hydrogen chloride gas were continuedfor three hours longer and then 50 ml of concentrated hydrochloric acidwas added. After cooling, white solids were collected and washed threetimes by water. Recrystallization from acetone gave 9.8 g of product(56.2%).¹H NMR (CDCl₃, 500 MHz) δppm: 6.98 (s, 2H), 4.61 (s, 4H), 3.94(s, 6H).

Example 92

Preparation of tetraethyl 2,5-bismethoxyl-p-xylene phosphonate (102).2,5-Bis-(chloromethyl)-1,4-dimethoxybenzene (101) (7.15 g, 30.2 mmol)and triethyl phosphite (60 ml) were heated to reflux for 24 hours. Afterremoval of unreacted triethyl phosphite under reduced pressure, 100 mlof hexanes were added to the mixture. The white solid was collected byfiltration, washed three times with hexanes, dried in vacuo and isolatedin 94.3% (12.48 g) yield.¹H NMR (CDCl₃, 500 MHz) δppm: 6.91 (s, 2H,ArH), 4.02 (m, 8H, CH₂), 3.93 (t, J=6.0 Hz, 4H, CH₂), 3.22 (d, J=20.0Hz, 4H, CH₂), 1.75 (m, 4H, CH₂), 1.48 (m, 4H, CH₂), 1.24 (t, J=7.0 Hz,12H, CH₃), 0.97 (t, J=7.2 Hz, 6H, CH₃)

Example 93

Preparation of diethyl4-{(E)-2-[4-(dibutylamino)phenyl}ethenyl}-2,5-dimethoxybenzylphosphonate(103). To a solution of diethyl 4-N,N-di-n-butylaminobenzaldehyde (1.80g, 7.725 mmol) and tetraethyl 2,5-bismethoxy-p-xylene phosphonate (102)(5.18 g, 11.8 mmol) in 100 ml of THF was added 1M of potassiumtert-butoxide (7.8 ml) in THF at 0° C. The mixture was stirred for 5 hat 0° C. and allowed to rise to ambient temperature. The reaction wasquenched by addition of 40 ml of water and the solvent was removed underreduced pressure. The product was purified by flash chromatography usingethyl acetate and ethyl acetate/methanol (8:2) as eluant and wasisolated in 57.8% (2.31 g) yield.

¹H NMR (CDCl₃, 500 MHz) δppm: 7.40 (d, J=9.0 Hz, 2H), 7.21 (d, J=16.0Hz, 1H, ═CH), 7.08 (s, 1H), 6.91 (d, J=3.0 Hz, 1H), 6.62 (d, J=9.0 Hz,2H), 4.05 (m, 4H, OCH₂), 3.87 (s, 3H, CH₃), 3.84 (s, 3H, CH₃), 3.23-3.32(m, overlap, 6H, CH₂N, CH₂PO), 1.59 (m, 4H, CH₂), 1.37 (m, 4H, CH₂),1.27 (t, J=7.0 Hz, 6H), 0.97 (t, J=7.0 Hz, 6H) ¹³C NMR (CDCl₃, 125.7MHz) δppm: 151.4, 150.5, 147.7, 129.0, 127.8, 126.8, 126.7, 124.9,119.1, 119.0, 118.0, 114.7, 114.6, 111.5, 61.9, 56.2, 50.7, 29.4, 27.2,26.1, 20.3, 16.4, 14.0.

Example 94

Preparation ofN-(4-{(E)-2-{4-[4-(1-tert-butoxycarbonyl)piperazin-1-yl]phenyl}ethenyl)-2,5-dimethoxyphenyl]ethenyl}phenyl)N,N-dibutylamine(104). To a solution of diethyl4-{(E)-2-[4-(dibutylamino)phenyl}ethenyl}-2,5-dimethoxybenzylphosphonate (103) (2.25 g, 4.35 mmol) and4-N-tert-butoxycarbonyl-piperazinobenzaldehyde (1.26 g, 4.35 mmol) in 50ml of THF was added 1M potassium tert-butoxide (4.5 ml) in THF at 0° C.The mixture was stirred for 5 h at 0° C. and allowed to rise to ambienttemperature. The reaction was quenched by addition of 40 ml of water.After removal of solvent under reduced pressure, the product waspurified by flash chromatography using ethyl acetate/hexanes (3:7) aseluant and isolated in 71.4% (2.03 g) yield.

¹H NMR (CDCl₃, 500 MHz) δppm: 7.47 (d, J=9.0 Hz, 2H), 7.42 (d, J=8.5Hz), 7.34 (d, J=16.5 Hz, 1H), 7.25 (d, J=16.0 Hz, 1H, ═CH, overlap withsolvent peak), 7.12 (s, 1H), 7.11 (s, 1H),7.04 (d, J=16.5 Hz, 1H, ═CH),7.03 (d, J=16.5 Hz, 1H, ═CH), 6.91 (d, J=9.0 Hz, 2H), 6.63 (d, J=8.5 Hz,2H), 3.92 (s, 3H, CH₃), 3.91 (s, 3H, CH₃), 3.60 (t, J=4.5 Hz, 4H, CH₂),3.30 (t, J=7.5 Hz, 4H, CH₂), 3.18 (s, br, 4H, CH₂), 1.59 (m, 4H, CH₂),1.38 (m, 4H, CH₂), 0.97 (t, J=7.5 Hz, 6H) ¹³C NMR (CDCl₃, 125.7 MHz)δppm: 154.7, 151.3, 151.1, 150.3. 147.7, 130.0, 128.9, 127.8, 127.5,127.2, 125.7, 125.0, 120.7, 118.0, 116.3, 111.5, 108.9, 108.4, 79.9,56.5, 56.4, 50.8, 49.1, 29.5, 28.4, 20.3, 14.0 (2 carbons was notobserved)

HRMS (FAB) Calcd. For C₄₁H₅₅N₃O₄: M⁺653.42. Found 653.4193.

Anal. Calcd. For C₄₁H₅₅N₃O₄: C, 75.31; H, 8.48;. N, 6.43. Found: C,75.08; H, 8.78; N, 6.44.

Example 95

Preparation of4-N,N-{2,5-dimethoxy-4-[(E)-2-(4-piperazin-1-ylphenyl)ethenyl]phenyl}ethenyl)aniline(105). To a solution ofN-(4-{(E)-2-{4-[4-(1-tert-butoxycarbonyl)piperazin-1-yl]phenyl}ethenyl)-2,5-dimethoxyphenyl]ethenyl}phenyl)N,N-dibutylamine(104) (1.53 g, 2.34 mmol) in 50 ml of THF was added 15 ml of 2Mhydrochloric acid. The mixture was heated to reflux for 6 h and allowedto cool to room temperature. The solution was neutralized with asolution of sodium hydroxide and extracted three times withether/methylene chloride (4:1). The combined organic layer was driedover anhydrous magnesium sulfate. After removal of solvent, the productwas purified by recrystallization from toluene/hexanes to give a yieldof 85.7% (1.11 g).¹H NMR (CDCl₃, 500 MHz) δppm: 7.47 (d, J=8.5 Hz, 2H),7.41 (d, J=9.0 Hz), 7.34 (d, J=16.5 Hz, 1H), 7.25 (d, J=16.0 Hz, 1H,═CH, overlap with solvent peak), 7.11 (s, 1H), 7.10 (s, 1H), 7.04 (d,J=16.5 Hz, 1H, ═CH), 7.02 (d, J=16.5 Hz, 1H, ═CH), 6.91 (d, J=9.0 Hz,2H), 6.63 (d, J=8.5 Hz, 2H), 3.92 (s, 3H, CH₃), 3.91 (s, 3H, CH₃), 3.30(t, J=7.5 Hz, 4H, CH₂), 3.20 (t, br, 4H, CH₂), 3.05 (t, br, 4H, CH₂),1.59 (m, 4H, CH₂), 1.37 (m, 4H, CH₂), 0.97 (t, J=7.5 Hz, 6H)¹³C NMR(CDCl₃, 125.7 MHz) δppm: 151.3, 151.1, 151.0, 129.4, 128.9, 128.0,127.8, 127.4, 127.1, 125.9, 125.0, 120.4, 118.0, 115.8, 111.5, 108.8,108.5, 56.5, 56.4, 50.8, 50.1, 46.1, 29.5, 20.3, 14.0

HRMS (FAB): calcd C₃₆H₄₇N₃O₂. For M⁺553.37, found for [M+H]⁺554.3748.

Anal. Calcd. C₃₆H₄₇N₃O₂ For: C, 78.08; H, 8.55;. N, 7.59. Found: C,78.40; H, 8.65; N, 7.70.

Example 96

Preparation of[4-(4-{4-[(E)-2-(4-{(E)-2-[4-(dibutylamino)phenyl]ethenyl}-2,5-dimethoxyphenyl)ethenyl]phenyl}piperazin-1-yl)phenyl](diphenyl)sulfoniumhexafluorophosphate (106). A mixture of4-N,N-{2,5-dimethoxy-4-[(E)-2-(4-piperazin-1-ylphenyl)ethenyl]phenyl}ethenyl)aniline(105) and 4-fluorotriphenylsulfonium hexafluorophosphate (0.46 g, 1.08mmol) in 5 ml of N,N-dimethyl sulfoxide was heated to 100° C. for 6hours. Upon cooling to ambient temperature, the mixture was poured intoa 5% aqueous solution of potassium hexafluorophosphate. The yellow solidwas collected by filtration and washed three times with the abovesolution. The product was purified by flash chromatography using neutralalumina and methylene chloride/methanol as eluant. ¹H NMR (CDCl₃, 500MHz) δ ppm: 7.69 (t, br, J=7.2 Hz, 2H), 7.65 (t, J=8.0 Hz, 4H), 7.56 (d,J=8.0 Hz, 4H), 7.53 (d, J=9.0 Hz, 2H), 7.46 (d, J=9.0 Hz, 2H), 7.41 (d,J=8.5 Hz, 2H), 7.33 (d, J=16.5 Hz, 1H, ═CH), 7.25 (d, J=16.5 Hz, 1H,═CH), 7.0-7.15 (m, 6H), 6.87 (d, J=9.0 Hz, 2H), 6.62 (d, J=8.5 Hz, 2H),3.91 (s, 3H, CH₃), 3.89 (s, 3H, CH₃), 3.56 (t, br, 4H, CH₂), 3.34 (t,br, 4H, CH₂), 3.92 (t, J=7.5 Hz, 4H), 1.58 (m, 4H, CH₂), 1.36 (m, 4H,CH₂), 0.96 (t, J=7.2 Hz, 6H, CH₃).¹³C NMR (CDCl₃, 125.7 MHz) δppm:154.5, 151.3, 151.1, 149.6, 147.7, 134.1, 133.3, 131.4, 130.1, 129.9,129.0, 127.8, 127.5, 126.1, 125.7, 125.0, 120.7, 117.9, 115.8, 115.7,111.5, 108.9, 108.4, 105.7, 56.5, 56.4, 50.7, 48.2, 46.4, 29.5, 20.3,14.0

HRMS (FAB) Calcd. For C₅₄H₆₀N₃O₂S: M⁺814.44. Found 814.4418.

Anal. Calcd. C₅₄H₆₀N₃O₂SPF₆ For: C, 67.55; H, 6.30;. N, 4.38. Found: C,67.47; H, 6.22; N, 4.44.

Example 97

Preparation ofE,E-1,4-bis[4′-piperazino-(N-tert-butoxycarbonyl)styryl]benzene (107).To a solution of N-tert-butoxycarbonyl-N′-(p-formylphenyl)piperazine(2.0 g, 6.89 mmol) and tetraethyl 2,5-bis(butoxyl)-p-xylene phosphonate(1.79 g, 3.43 mmol) in 50 ml of THF was added 1M KO^(t)Bu (7 ml, 7 mmol)at 0° C. The mixture was stirred at 0° C. for 2 hours. The reaction wasquenched by addition of 50 ml of water. The yellow solid was collectedby filtration and washed three times with methanol; the yield was 91.7%(2.50 g).¹H NMR (500 MHz, CDCl₃) δppm: 7.45 (d, J=8.5 Hz, 4H), 7.34 (d,J=16.0 Hz, 2H, ═CH), 7.10 (s, 2H), 7.05 (d, J=16.0 Hz, 2H, ═CH), 6.92(d, J=8.5 Hz, 4H), 4.05 (t, J=6.5 Hz, 4H), 3.60 (m, 8H, NCH₂), 3.20 (m,8H, NCH₂), 1.85 (m, 4H, CH₂), 1.57 (m, 4H, CH₂), 1.49 (s, 18H, CH₃),1.02 (t, 6H, CH₃).

Example 98

Preparation of E,E-1,4-bis[4′-piperazinostyryl]benzene (108). 2M HCl(2.5 ml) was added to a solution ofE,E-1,4-bis[4′-piperazino-(N-tert-butoxycarbonyl)styryl]benzene (0.68 g,0.86 mmol) in 30 ml of THF at 0° C. The mixture was refluxed for 2hours. The reaction mixture was allowed to cool to ambient temperatureand the pH adjusted to 13-14 with an aqueous solution of sodiumhydroxide. The aqueous layer was extracted three times with 20 ml ofether, and the combined organic layer was washed three times with 20 mlof saturated brine and dried over anhydrous sodium sulfate. Afterremoval of solvent, the residue was recrystallized from toluene and wasisolated in 0.21 g (41.3%) yield. ¹H NMR (500 MHz, CDCl₃) δppm: 7.45 (d,J=8.5 Hz, 4H), 7.34 (d, J=16.5 Hz, 2H, ═CH), 7.10 (s, 2H), 7.06 (d,J=16.0 Hz, 2H, ═CH), 6.92 (d, J=9.0 Hz, 4H), 4.05 (t, J=6.5 Hz, 4H),3.20 (m, 8H, NCH₂), 3.05 (m, 8H, NCH₂), 1.86 (m, 4H, CH₂), 1.59 (m, 4H,CH₂), 1.03 (t, J=7.5 Hz, 6H, CH₃)¹³C NMR (125.7 MHz, CDCl₃) δppm: 151.0,150.8, 129.5, 128.2, 127.4, 126.8, 120.6, 115.8, 110.3, 69.2, 50.0,46.1, 31.6, 19.4, 14.0.

Example 99

Preparation of Compound 109. To a solution of julolidinecarboxaldehyde(201 mg, 1 mmol) and (julolidinylmethyl)triphenylphosphonium iodide (691mg, 1.2 mmol) in anhydrous CH₂Cl₂ (50 mL) was added potassiumtert-butoxide (168 mg, 1.5 mmol). The suspension was stirred overnightat room temperature while protected from light and moisture. Water wasadded and the mixture was extracted with methylene chloride. The solventwas removed and the precipitate was recrystallized from ethanol to givethe product in 64% yield.

¹H NMR (500 MHz, d₆-Acetone) δ ppm: 6.87 (s, 4H), 6.69 (s, 2H), 3.14 (t,³J(H,H)=5.6 Hz, 8H), 2.72 (t, ³J(H,H)=6.4 Hz, 8H), 1.94 (quint,³J(H,H)=5.9 Hz, 8H) HRMS (FAB) calcd for C₂₆H₃₀N₂: 370.2409 (M⁺), found:370.2390.

Example 100

Preparation of Compound 110. To a solution of julolidinecarboxaldehyde(402 mg, 2 mmol) and tetraethyl 2,5-dicyano-p-xylene phosphonate (428mg, 1 mmol) in anhydrous THF (50 mL) was added potassium tert-butoxide(500 mg, 2.2 mmol). The suspension was stirred at room temperature for20 hours while protected from light and moisture. The suspension wasfiltered through a bed of Celite which was rinsed with methylenechloride. The solvent was removed and the precipitate was recrystallizedfrom ethanol to give the product in 60% yield.

¹H NMR (250 MHz, CDCl₃) δppm: 7.94 (s, 2H), 7.15 (d, ³J(H,H)=16.0 Hz,2H), 7.08 (d, ³J(H,H)=15.9 Hz, 2H), 7.07 (s, 4H), 3.26 (t, ³J(H,H)=5.7Hz, 8H), 2.82 (t, ³J(H,H)=6.3 Hz, 8H), 2.02 (quint, ³J(H,H)=5.7 Hz, 8H).HRMS (FAB) calcd for C₃₆H₃₄N₄: 522.2783 (M⁺), found: 522.2773.

Example 101

Preparation of Compound 111. To a solution of terephthaldicarboxaldehyde(134 mg, 1 mmol) (julolidinylmethyl)triphenylphosphonium iodide (1.4 g,2.5 mmol) in anhydrous CH₂Cl₂ (50 mL) was added potassium tert-butoxide(500 mg, 4 mmol). The suspension was stirred at room temperature for 20hours while protected from light and moisture. Toluene and water wereadded to the suspension. The solution was extracted with toluene. Thesolution was dried under sodium sulfate and the solvent was removed. Thecrude product was obtained in 52% yield after purification by silica gelcolumn chromatography, eluting with methylene chloride.

¹H NMR (500 MHz, CDCl₃) δ ppm: 7.40 (s, 4H), 6.98 (s, 4H), 6.94 (d,³J(H,H)=16.1 Hz, 2H), 6.83 (d, ³J(H,H)=16.1 Hz, 2H), 3.17 (t,³J(H,H)=5.1 Hz, 8H), 2.78 (t, ³J(H,H)=6.4 Hz, 8H), 1.99 (quint,³J(H,H)=5.6 Hz, 8H). Anal. calcd C₃₄H₃₆N₂+0.14 CH₂Cl₂: C, 84.38, H,7.53, N, 5.76, found: C, 84.38, H, 7.61, N, 5.65. HRMS (FAB) calcd forC₃₄H₃₆N₂: 472.2878 (M⁺), found: 472.2878.

Example 102

Photopolymerizations initiated by one-photon excitation. Aliquots (1.25ml) of a 10 ml of solution containing 0.0791 mmol of sulfonium salt,such as 7, 8, 9, 23, 41, 52, or 61 and 8 ml of cyclohexene oxide (7.76g, 0.0791 mol) in methylene chloride were sealed in 4-ml Pyrex vialswith caps and irradiated with a 419 nm photochemical lamp in amerry-go-round holder. After various intervals the sample tubes werewithdrawn from the irradiation chamber and any ionic reactions wereimmediately quenched by the addition of 2M ammonia solution in methanol(1 ml). The polymers were precipitated by addition to methanol,collected by filtration and dried in vacuo for 40 hours. The plots oftime versus conversion is shown in FIG. 3 and 4 (above) demonstrate thateach of the salts described in this example of efficient initiators forcationic polymerization.

Example 103

Photochemical generation of acid in solution by one-photon excitationand determination of the photochemical quantum yield for compounds 23,41, and 52. The quantum yield for photochemical generation of acid,φ_(H) ₊ , was obtained from measurements of the acid generated when a4.0×10⁻⁴ M solution of a PAG in acetonitrile was one-photon excited byirradiation at 400 nm using either the monochromated output of a xenonlamp or a frequency-doubled mode-locked Ti:sapphire laser. At thisconcentration more than 99% of the incident photons were absorbed. Thephotogenerated acid was titrated by the addition of excess rhodamine Bbase in acetonitrile (6.0×10⁻⁵ M after addition) and quantifiedspectrophotometrically from the absorbance of protonated rhodamine Bbase. The acid-generation quantum yields were φ_(H) ₊ =0.55±0.05,0.44±0.04, and 0.013±0.002 for 23, 41, and 52, respectively.

Example 104

Photochemical generation of acid in solution by two-photon excitation ofcompound 41. Samples of 41 in acetonitrile (4.0×10⁻⁴ M) were excited in1-cm path-length fluorescence cells using focused (f=75 mm) 80-fs pulsesfrom a CW mode-locked Ti:sapphire laser (82-MHz, 8.5-mm diameterspot-size at lens). The two-photon-excitation (TPE) spectrum wasrecorded using the two-photon-fluorescence method with fluorescein inwater (1.54×10⁻⁵ M, pH=11) as a reference. The up-converted fluorescencewas detected at 520 nm and its intensity was proportional to the squareof the excitation power, as expected for two-photon absorption (TPA).The concentration of the photogenerated acid, [H⁺], was determinedspectrophotometrically following a 30-minute exposure. The relativeacid-yield efficiency at each wavelength was calculated by dividing [H⁺]by the ratio of the emission counts and the TPE action cross-section ofthe fluorescein reference (<F(t)>/φ_(f)δ)_(ref) (to account for thetemporal and spatial dependence of the excitation intensity as afunction of wavelength) and normalizing to δ of 41 at 705 nm. The TPEand the acid-yield efficiency spectra are shown in FIG. 7. The inset isa plot of the acid-yield versus two-photon-excitation power at 745 nm.41 exhibits strong TPA from 705-850 nm (δ>100 GM) that appears to peaknear 710 nm (δ=690 GM), consistent with measurements obtained forsimilar bis[(diarylamino)styryl]benzenes. The T?E and acid-yieldefficiency spectra exhibit similar features, and the acid-yield at 745nm increases quadratically with excitation power, as expected for aphotochemical process activated by TPA.

Example 105

Comparison of compounds 23 and 41 with conventional PAGs for sensitivitytoward two-photon-initiated polymerization of the liquid epoxide resinsAraldite CY179MA and 4-vinyl-1-cyclohexene diepoxide. The epoxidepolymerization sensitivity of 23 and 41 under near-infrared excitationwas compared with that of four widely-used conventional PAGs (FIG. 8):CD1012, CD1012/ITX (1:1.6 molar ratio), TPS, and DPI-DMAS. Test resinsof each initiator (10 mM) in Araldite CY179MA (Ciba,7-oxabicyclo[4.1.0]heptane-3-carboxylic acid,7-oxabicyclo[4.1.0]hept-3-ylmethyl ester) and 4-vinyl-1-cyclohexenediepoxide were irradiated with focused (f=75 mm) 80-fs pulses from aTi:sapphire laser (82-MHz repetition rate, 0.94-mm diameter spot-size atlens). The threshold power for the onset of polymerization within a10-second exposure was established at 710 and 760 nm by the advent of acircular diffraction pattern in the far-field of the transmitted beam.Exposure at higher powers and for longer times produced clearly visiblesolid features of cross-linked polymer. In Araldite using 710-nmexcitation, the threshold powers were 2.4 mW (41), 44 mW (CD1012/ITX),and 212 mW (CD1012). The available power (317 mW) was insufficient toinitiate polymerization of the TPS and DPI-DMAS resins. In Aralditeusing 760-nm excitation, the threshold powers were 5.6 mW (41), 50 mW(CD1012/ITX), 468 mW (DPI-DMAS), and 560 mW (CD1012). The availablepower (655 mW) was not adequate to initiate polymerization of the TPSresin. In 4-vinyl-1-cyclohexene diepoxide using 710-nm excitation, thethreshold powers were 1.7 mW (41), 4.4 mW (23), 33 mW (CD1012/ITX), and185 mW (CD1012). The available power (317 mW) was insufficient toinitiate polymerization of the TPS and DPI-DMAS resins. In4-vinyl-1-cyclohexene diepoxide using 760-nm excitation, the thresholdpowers were 4.7 mW (41), 6.4 mW (23), and 45 mW (CD1012/ITX). Theavailable power (655 mW) was not adequate to initiate polymerization ofthe CD1012, DPI-DMAS, and TPS resins. The threshold measurements showthat the two-photon sensitivity of 23 and 41 is nearly one order ofmagnitude greater than that of the best-performing conventionalinitiator, (CD1012/ITX), and more than two orders of magnitude greaterthan that of TPS.

Example 106

Fabrication of three-dimensional microstructures in a solid epoxideresin containing compound 41 using femtosecond laser pulses. In thedark, 393 mg of EPON SU-8 (Shell), 262 mg of γ-butyrolactone, and 10.2mg of 41 (2.5 wt.-% in resin) were stirred until the solids haddissolved. The resin mixture was blade-casted onto a substrate treatedwith a trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane adhesionpromoter at a thickness of 510 μm, dried in air at room temperature for10 days, then heated on a hot-plate at 100° C. for 15 minutes. Theresulting solid film had a thickness of 330±100 μm. The film was exposedin a target three-dimensional pattern by tightly focusing 80-fs pulsesfrom a Ti:sapphire laser at a wavelength of 745 nm into the resin whiletranslating the focal point at a speed of 50 μm/s (60×/1.4 N.A.oil-immersion objective, 82-MHz pulse repetition rate). The averageoptical power at the film was varied between 1-5 mW. Followingirradiation, the film was immersed in γ-butyrolactone for 60 minutes toremove the unexposed resin, and then rinsed with methanol, leaving themicrostructures shown in FIG. 9 standing freely on the substrate.

Example 107

Two-photon polymerization of a solid epoxide resin containing PAG 41using femtosecond laser pulses and measurement of the polymerizationthreshold power. In the dark, 200 mg of EPON SU-8, 133 mg ofγ-butyrolactone, and 2 mg of 41 (1 wt.-% in resin) were stirred untilthe solids had dissolved. The resin mixture was blade-casted onto asubstrate treated with atrimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane adhesionpromoter at a thickness of 510 μm, dried in air at room temperature for10 days, then heated on a hot-plate at 100° C. for 15 min. The resultingsolid film had a thickness of 330±100 μm. The film was exposed in atarget three-dimensional test-pattern by tightly focusing 70-fs pulsesfrom a Ti:sapphire laser at a wavelength of 730 mn into the resin whiletranslating the focal point at a speed of 50 μm/s (60×/1.4 N.A.oil-immersion objective, 82-MHz pulse repetition rate). Followingirradiation, the film was immersed in γ-butyrolactone for 60 minutes toremove the unexposed resin, and then rinsed with methanol, leavingfree-standing microstructures where the average exposure power wassuitably high. Inspection of the sample before and after developing withγ-butyrolactone revealed that the resin was damaged for average opticalpowers exceeding 17±2 mW, and the threshold power for polymerization was0.3±0.1 mW.

Example 108

Two-photon polymerization of a solid epoxide resin containing compound52 using femtosecond laser pulses and measurement of the polymerizationthreshold power. In the dark, 200 mg of EPON SU-8, 142 mg ofγ-butyrolactone, and 5 mg of 52 (2.5 wt.-% in resin) were stirred untilthe solids had dissolved. The resin mixture was blade-casted onto asubstrate treated with atrimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane adhesionpromoter at a thickness of 510 μm, dried in air at room temperature for10 days, then heated on a hot-plate at 100° C. for 15 min. The resultingsolid film had a thickness of 330±100 μm. The film was exposed in atarget three-dimensional test-patent by tightly focusing 70-fs pulsesfrom a Ti:sapphire laser at a wavelength of 730 nm into the resin whiletranslating the focal point at a speed of 50 μm/s (60×/1.4 N.A.oil-immersion objective, 82-MHz pulse repetition rate). Followingirradiation, the film was immersed in γ-butyrolactone for 60 minutes toremove the unexposed resin, and then rinsed with methanol, leavingfree-standing microstructures where the average exposure power had beensuitably high. Inspection of the sample before and after developing withγ-butyrolactone revealed that the resin was damaged for average opticalpowers exceeding 17±2 mW, and the threshold power for polymerization was1.3±0.3 mW.

Example 109

Two-photon polymerization of a solid epoxide resin containing compound23 using femtosecond laser pulses and measurement of the polymerizationthreshold power. In the dark, 200 mg of EPON SU-8, 140 mg ofγ-butyrolactone, and 4.7 mg of 52 (2.4 wt.-% in resin) were stirreduntil the solids had dissolved. The resin mixture was blade-casted ontoa substrate treated with atrimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane adhesionpromoter at a thickness of 510 μm, dried in air at room temperature for10 days, then heated on a hot-plate at 100° C. for 15 min. The resultingsolid film had a thickness of 230±100 μm. The film was exposed in atarget three-dimensional test-pattern by tightly focusing 70-fs pulsesfrom a Ti:sapphire laser at a wavelength of 720 nm into the resin whiletranslating the focal point at a speed of 50 μm/s (60×/1.4 N.A.oil-immersion objective, 82-MHz pulse repetition rate). Followingirradiation, the film was immersed in γ-butyrolactone for 60 minutes toremove the unexposed resin, and then rinsed with methanol, leavingfree-standing microstructures where the average exposure power wassuitably high. Inspection of the sample before and after developing withγ-butyrolactone revealed that the resin was damaged for average opticalpowers exceeding 17±2 mW, and the threshold power for polymerization was˜7 mW.

Example 110

Fabrication of sub-millimeter columnar structures by two-photonpolymerization of a liquid epoxide resin containing PAG 41 usingnanosecond laser pulses. A cell was fashioned by sandwiching a 2-mmthick o-ring between two glass substrates, one of which was treated witha trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane adhesionpromoter. The cell was filled with 10.3 mM 41 in 20%/80% EPONSU-8/4-vinyl-1-cyclohexene diepoxide (1.26 wt.-% PAG). Several regionsof the cell were then irradiated for 5 s using focused 4.0-mJ 5-ns laserpulses at a wavelength of 745 nm (10-Hz repetition rate; 500-mm focallength lens; 6-mm beam diameter at the lens). Columns of cross-linkedpolymer that spanned the length of the cell formed in the irradiatedregion. Following exposure, the cell was disassembled and rinsed withpropylene glycol methylether acetate. Free-standing columns oftwo-photon cross-linked polymer remained on the adhesion-promotedsubstrate. The width of the columns was typically 200 μm.

Example 111

Fabrication of columnar structures by two-photon-induced polymerizationof a liquid epoxide resin containing compound 41 using nanosecond laserpulses and measurement of the polymerization threshold energy. A cellwas fashioned by sandwiching a 2-mm thick o-ring between two glasssubstrates, one of which was treated with atrimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane adhesionpromoter. The cell was filled with 10 mM 41 in 20%/80% EPONSU-8/4-vinyl-1-cyclohexene diepoxide (1.3 wt.-% PAG). Several regions ofthe film were then irradiated with focused 5-ns laser pulses at awavelength of 745 mn (10-Hz repetition rate; 500-mm focal length lens;5-mm beam diameter at the lens). The onset of two-photon-inducedpolymerization was marked by the appearance of a ringed diffractionpattern in the far-field transmitted beam. Extensive cross-linkingultimately resulted in disruption of the far-field pattern and formationof a column of cross-linked polymer that spanned the length of the cellin the irradiated region. The onset of polymerization occurred at pulseenergies of 2.1 ml, 1.4 mJ, 0.9 mn, and 0.9 ml for exposure times of 1s, 2 s, 3 s, and 5 s, respectively. Following exposure, the cell wasdisassembled and rinsed with propylene glycol methylether acetate.Free-standing columns of two-photon cross-linked polymer remained on theadhesion-promoted substrate. FIG. 10 shows a scanning electronmicrograph of the columns. The width of the smallest feature was 60 μm.

Example 112

Fabrication of columnar structures by two-photon-induced polymerizationof a solid epoxide resin containing compound 41 using nanosecond laserpulses and measurement of the polymerization threshold energy. In thedark, 1 g of EPON SU-8, 660 mg of γ-butyrolactone, and 10.2 mg of 41 (1wt.-% in resin) were stirred until the solids had dissolved. The resinmixture was blade-casted onto a substrate treated with atrimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane adhesionpromoter at a thickness of 510 μm and heated on a hot-plate at 80° C.for 60 min. The resulting solid film had a thickness of 330±100 μm.Several regions of the film were then irradiated with focused 5-ns laserpulses at a wavelength of 745 nm (10-Hz repetition rate; 500-mm focallength lens; 5-mm beam diameter at the lens). The onset oftwo-photon-induced polymerization was marked by the appearance of aringed diffraction pattern in the far-field transmitted beam. Extensivecross-linking ultimately resulted in disruption of the far-field patternand formation of a visible feature in the film. The onset ofpolymerization occurred at pulse energies of 0.8 mJ, 0.6 mJ, 0.4 mJ, and0.2 mJ for exposure times of 1 s, 2 s, 3 s, and 5 s, respectively.Following exposure, the unpolymerized resin was removed by soaking thefilm in propylene glycol methylether acetate for 30 minutes.Free-standing columns of cross-linked polymer were present on thesubstrate in the irradiated regions.

The entire contents of each of the above-identified references, patents,applications and published applications are hereby incorporated byreference, the same as if set forth at length.

Obviously, numerous modifications and variations of the presentinvention are possible in light of the above teachings. It is thereforeto be understood that within the scope of the appended claims, theinvention may be practiced otherwise than as specifically describedherein.

1. A compound or composition, comprising: at least one chromophorehaving a simultaneous two-photon or multi-photon absorptivity; and atleast one photoacid or radical generator in close proximity to saidchromophore; wherein said chomophore has a two-photon absorptioncross-section of >50×10⁻⁵⁰ cm⁴ s/photon.
 2. The compound or compositionof claim 1, wherein said generator comprises at least one sulfonium,selenonium, or iodonium group, or other acid- or radical generatinggroup.
 3. The compound or composition of claim 1, wherein uponsimultaneous absorption of two or more photons, said chromophore adoptsan electronically excited state, and therefrom activates said generatorto generate a Brnsted or Lewis acid and/or radical.
 4. The compound orcomposition of claim 1, wherein said generator comprises at least oneanion selected from the group consisting of F⁻, Cl⁻, Br⁻, I⁻, CN⁻, SO₄²⁻, PO₄ ³⁻, CH₃CO₂ ⁻, CF₃SO₃ ⁻, NO₂ ⁻, NO₃ ⁻, BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻, AsF₆⁻, SbCl₄ ⁻, ClO₃ ⁻, ClO₄ ⁻, and B(aryl)₄ ⁻, where aryl is an aryl groupcontaining 25 or fewer carbon atoms that may be optionally substitutedwith one or more alkyl groups, aryl groups or halogens.
 5. The compoundor composition of claim 1, wherein said generator is brought into closeproximity with said chromophore by at least one mechanism selected fromthe group consisting of covalent linkage, ion-pairing, hydrogen-bonding,charge-transfer complex formation, perfluoroaryl-aryl electrostaticinteraction, π-stacking association, coordinative-bond formation,dipole-dipole pairing, and combinations thereof.
 6. The compound orcomposition of claim 1, wherein the chromophore and the generator arecovalently linked, and wherein the chromophore is a molecule having astructure selected from the group consisting of D-π-D, D-A-D, A-π-A andA-D-A, where D is an electron donor and A is an electron acceptor. 7.The compound or composition of claim 1, wherein the sulfonium group hasthe formula —(CH₂)_(γ)—(C₆H₄)_(δ)—SR_(a5)R_(a6), wherein R_(a5) andR_(a6) are each independently alkyl, aryl, or monomer groups, andwherein γ=0 to 25, and δ=0 to
 5. 8. The compound or composition of claim1, wherein the selenonium group has the formula—(CH₂)_(γ)—(C₆H₄)_(δ)—SeR_(a5)R_(a6), wherein R_(a5) and R_(a6) are eachindependently alkyl, aryl, or monomer groups, and wherein γ=0 to 25, andδ=0 to
 5. 9. The compound or composition of claim 1, wherein theiodonium group has the formula —(CH₂)_(γ)—(C₆H₄)_(δ)—IR_(a7), whereinR_(a7) is alkyl, aryl, or monomer group, and wherein γ=0 to 25, and δ=0to
 5. 10. The compound or composition of claim 1, which has thestructure:

wherein X═S or Se and n=0, 1, 2, 3, 4, or 5, wherein Ar₁ and Ar₂ areeach independently a 5-membered heteroaromatic ring; a 6-memberedaromatic ring; or a 6-membered heteroaromatic ring, wherein each of Ar₁and Ar₂ are optionally independently substituted with one or more H,alkyl group, alkoxy group, or aryl group, which groups may be optionallyindependently substituted with one or more sulfonium, selenonium, oriodonium groups; other acid- or radical-generating species; or monomeror pre-polymer groups, wherein R₁, R₂, R₃, and R₄ are each independentlyalkyl or aryl groups, which groups may be optionally independentlysubstituted one or more sulfonium, selenoniumn, or iodonium groups;other acid- or radical-generating species; or monomer or pre-polymergroups, wherein Y is an anion selected from the group consisting of F⁻,Cl⁻, Br⁻, I⁻, CN⁻, SO₄ ²⁻, PO₄ ³⁻, CH₃CO₂ ⁻, CF₃SO₃ ⁻, NO₂ ⁻, NO₃ ⁻, BF₄⁻, PF₆ ⁻, SbF₆ ⁻, AsF₆ ⁻, SbCl₄ ⁻, ClO₃ ³¹, ClO₄ ⁻, and B(aryl)₄ ⁻,where aryl is an aryl group containing 25 or fewer carbon atoms that maybe optionally substituted with one or more alkyl groups, aryl groups orhalogens, wherein z is an integer equal to the charge of the chromophoreportion of the compound, wherein p is an integer equal to the charge onthe anion, and wherein q and Q are integers such that the relationshipzQ=pq is satisfied.
 11. The compound or composition of claim 1, whichhas the structure:

wherein X═I and n=0, 1, 2, 3, 4, or 5, wherein Ar₁ and Ar₂ are eachindependently a 5-membered heteroaromatic ring; a 6-membered aromaticring; or a 6-membered heteroaromatic ring, wherein each of Ar₁ and Ar₂are optionally independently substituted with one or more H, alkylgroup, alkoxy group, or aryl group, which groups may be optionallyindependently substituted with one or more sulfonium, selenonium, oriodonium groups; other acid- or radical-generating species; or monomeror pre-polymer groups, wherein R₁ and R₂ are each independently alkyl,or aryl groups, which groups may be optionally independently substitutedwith one or more sulfonium, selenonium, or iodonium groups; other acid-or radical-generating species; or monomer or pre-polymer groups, whereinY is an anion selected from the group consisting of F⁻, Cl⁻, Br⁻, I⁻,CN⁻, SO₄ ²⁻, PO₄ ³⁻, CH₃CO₂ ⁻, CF₃SO₃ ⁻, NO₂ ⁻, NO₃ ⁻, BF₄ ⁻, PF₆ ⁻,SbF₆ ⁻, AsF₆ ⁻, SbCl₄ ⁻, ClO₃ ⁻, ClO₄ ⁻, and B(aryl)₄ ⁻, where aryl isan aryl group containing 25 or fewer carbon atoms that may be optionallysubstituted with one or more alkyl groups, aryl groups or halogens,wherein z is an integer equal to the charge of the chromophore portionof the compound, wherein p is an integer equal to the charge on theanion, and wherein q and Q are integers such that the relationship zQ=pqis satisfied.
 12. The compound or composition of claim 1, which has thestructure:

wherein X is O and n=1, 2, 3, 4, or 5, wherein Ar₁ and Ar₂ are eachindependently a 5-membered heteroaromatic ring; a 6-membered aromaticring; or a 6-membered heteroaromatic ring, wherein each of Ar₁ and Ar₂are optionally independently substituted with one or more H, alkylgroup, alkoxy group, or aryl group, which groups may be optionallyindependently substituted with one or more sulfonium, selenonium, oriodonium groups; other acid- or radical-generating species; or monomeror pre-polymer groups, wherein R₁ and R₂ are each independently H,alkyl, or aryl groups, which groups may be optionally independentlysubstituted with one or more sulfonium, selenonium, or iodonium groups;other acid- or radical-generating species; or monomer or pre-polymergroups, wherein at least one of Ar₁, Ar₂, R₁ or R₂ is substituted withone or more sulfonium, selenonium, or iodonium groups, or other acid- orradical generating groups, wherein Y is an anion selected from the groupconsisting of F⁻, Cl⁻, Br⁻, I⁻, CN⁻, SO₄ ²⁻, PO₄ ³⁻, CH₃CO₂ ⁻, CF₃SO₃ ⁻,NO₂ ⁻, NO₃ ⁻, BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻, AsF₆ ⁻, SbCl₄ ⁻, ClO₃ ⁻, ClO₄ ⁻, andB(aryl)₄ ⁻, where aryl is an aryl group containing 25 or fewer carbonatoms that may be optionally substituted with one or more alkyl groups,aryl groups or halogens, wherein z is an integer equal to the charge ofthe chromophore portion of the compound, wherein p is an integer equalto the charge on the anion, and wherein q and Q are integers such thatthe relationship zQ=pq is satisfied.
 13. The compound or composition ofclaim 1, which has the structure:

wherein X is N and n=0, 1, 2, 3, 4, or 5, wherein Ar₁ and Ar₂ are eachindependently a 5-membered heteroaromatic ring; a 6-membered aromaticring; or a 6-membered heteroaromatic ring, wherein each of Ar₁ and Ar₂are optionally independently substituted with one or more H, alkylgroup, alkoxy group, or aryl group, which groups may be optionallyindependently substituted with one or more sulfonium, selenonium, oriodonium groups; other acid- or radical-generating species; or monomeror pre-polymer groups, wherein R₁, R₂, R₃, and R₄ are each independentlyH, alkyl group, or aryl group, which groups may be optionallyindependently substituted with one or more sulfonium, selenonium, oriodonium groups; other acid- or radical-generating species; or monomeror pre-polymer groups, wherein at least one of Ar₁, Ar₂, R₁, R₂, R₃, orR₄ is substituted with one or more sulfonium, selenonium, or iodoniumgroups, or other acid- or radical generating groups, wherein Y is ananion selected from the group consisting of F⁻, Cl⁻, Br⁻, I⁻, CN⁻, SO₄²⁻, PO₄ ³⁻, CH₃CO₂ ⁻, CF₃SO₃ ⁻, NO₂ ⁻, NO₃ ⁻, BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻, AsF₆⁻, SbCl₄ ⁻, ClO₃ ⁻, ClO₄ ⁻, and B(aryl)₄ ⁻, where aryl is an aryl groupcontaining 25 or fewer carbon atoms that may be optionally substitutedwith one or more alkyl groups, aryl groups or halogens, wherein z is aninteger equal to the charge of the chromophore portion of thecomposition, wherein p is an integer equal to the charge on the anion,and wherein q and Q are integers such that the relationship zQ=pq issatisfied.
 14. The compound or composition of claim 1, which has thestructure:

wherein X is I, n=0, 1, 2, 3, 4, or 5, and n′=0, 1, 2, 3, 4 or 5,wherein Ar₁ and Ar₂ are each independently a 5-membered heteroaromaticring; a 6-membered aromatic ring; or a 6-membered heteroaromatic ring,wherein Ar₃ is a 5-membered heteroaromatic ring; a 6-membered aromaticring; or a 6-membered heteroaromatic ring, wherein each of Ar₁ and Ar₂are optionally independently substituted with one or more H, alkylgroup, alkoxy group, or aryl group, which groups may be optionallyindependently substituted with one or more sulfonium, selenonium, oriodonium groups; other acid- or radical-generating species; or monomeror pre-polymer groups, wherein Ar₃ is optionally substituted with one ormore H, acceptor group, alkyl group, alkoxy group, aryl group, whichgroups may be optionally independently substituted with one or moresulfonium, selenonium, or iodonium groups; other acid- orradical-generating species; or monomer or pre-polymer groups, wherein R₁and R₂ are each independently alkyl group, or aryl group, which groupsmay be optionally independently substituted with one or more sulfonium,selenonium, or iodonium groups; other acid- or radical-generatingspecies; or monomer or pre-polymer groups, wherein Y is an anionselected from the group consisting of F⁻, Cl⁻, Br⁻, I⁻, CN⁻, SO₄ ²⁻, PO₄³⁻, CH₃CO₂ ⁻, CF₃SO₃ ⁻, NO₂ ⁻, NO₃ ⁻, BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻, AsF₆ ⁻,SbCl₄ ⁻, ClO₃ ⁻, ClO₄ ⁻; and B(aryl)₄ ⁻; where aryl is an aryl groupcontaining 25 or fewer carbon atoms that may be optionally substitutedwith one or more alkyl groups, aryl groups or halogens, wherein z is aninteger equal to the charge of the chromophore portion of the compound,wherein p is an integer equal to the charge on the anion, and wherein qand Q are integers such that the relationship zQ=pq is satisfied. 15.The compound or composition of claim 1, which has the structure:

wherein X is S or Se, n=0, 1, 2, 3, 4, or 5, and n′=0,1,2,3,4 or 5,wherein Ar₁ and Ar₂ are each independently a 5-membered heteroaromaticring; a 6-membered aromatic ring; or a 6-membered heteroaromatic ring,wherein Ar₃ is a 5-membered heteroaromatic ring; a 6-membered aromaticring; or a 6-membered heteroaromatic ring, wherein each of Ar₁ and Ar₂are optionally independently substituted with H, alkyl group, alkoxygroup, or aryl group, which groups may be optionally independentlysubstituted with one or more sulfonium, selenonium, or iodonium groups;other acid- or radical-generating species; or monomer or pre-polymergroups, wherein Ar₃ is optionally independently substituted with one ormore H, acceptor group, alkyl group, alkoxy group, aryl group, whichgroups may be optionally independently substituted with one or moresulfonium, selenonium, or iodonium groups; other acid- orradical-generating species; or monomer or pre-polymer groups, whereinR₁, R₂, R₃, and R₄ are each independently alkyl group, aryl group, whichgroups may be optionally independently substituted with one or moresulfonium, selenonium, or iodonium groups; other acid- orradical-generating species; or monomer or pre-polymer groups, wherein Yis an anion selected from the group consisting of F⁻, Cl⁻, Br⁻, I⁻, CN⁻,SO₄ ²⁻, PO₄ ³⁻, CH₃CO₂ ⁻, CF₃SO₃ ⁻, NO2⁻, NO₃ ⁻, BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻,AsF₆ ⁻, SbCl₄ ⁻, ClO₃ ⁻, ClO₄ ⁻; and B(aryl)₄ ⁻, where aryl is an arylgroup containing 25 or fewer carbon atoms that may be optionallysubstituted with one or more alkyl groups, aryl groups or halogens,wherein z is an integer equal to the charge of the chromophore portionof the compound, wherein p is an integer equal to the charge on theanion, and wherein q and Q are integers such that the relationship zQ=pqis satisfied.
 16. The compound or composition of claim 1, which has thestructure:

wherein X is O, n=0, 1, 2, 3, 4, or 5, and n′=0, 1, 2, 3, 4 or 5,wherein Ar₁ and Ar₂ are each independently a 5-membered heteroaromaticring; a 6-membered aromatic ring; or a 6-membered heteroaromatic ring,wherein Ar₃ is a 5-membered heteroaromatic ring; a 6-membered aromaticring; or a 6-membered heteroaromatic ring, wherein each of Ar₁ and Ar₂are optionally independently substituted with one or more H, alkylgroup, alkoxy group, aryl group, which groups may be optionallyindependently substituted with one or more sulfonium, selenonium, oriodonium groups; other acid- or radical-generating species; or monomeror pre-polymer groups, wherein Ar₃ is optionally substituted with one ormore H, acceptor group, alkyl group, alkoxy group, aryl group, whichgroups may be optionally independently substituted with one or moresulfonium, selenonium, or iodonium groups; other acid- orradical-generating species; or monomer or pre-polymer groups, wherein R₁and R₂ are each independently H, alkyl group, aryl group, which groupsmay be optionally independently substituted with one or more sulfonium,selenonium, or iodonium groups; other acid- or radical-generatingspecies; or monomer or pre-polymer groups, wherein at least one of Ar₁,Ar₂, Ar₃, R₁ or R₂ is substituted with one or more sulfonium,selenonium, or iodonium groups, or other acid- or radical generatinggroups, wherein Y is an anion selected from the group consisting of F⁻,Cl⁻, Br⁻, I⁻, CN⁻, SO₄ ²⁻, PO₄ ³⁻, CH₃CO₂ ⁻, CF₃SO₃ ⁻, NO₂ ⁻, NO₃ ⁻, BF₄⁻, PF₆ ⁻, SbF₆ ⁻, AsF₆ ⁻, SbCl₄ ⁻, ClO₃ ⁻, ClO₄ ⁻, and B(aryl)₄ ⁻, wherearyl is an aryl group containing 25 or fewer carbon atoms that may beoptionally substituted with one or more alkyl groups, aryl groups orhalogens, wherein z is an integer equal to the charge of the chromophoreportion of the compound, wherein p is an integer equal to the charge onthe anion, and wherein q and Q are integers such that the relationshipzQ=pq is satisfied.
 17. The compound or composition of claim 1, whichhas the structure:

wherein X is N, n=0, 1, 2, 3, 4 or 5, n′=0, 1, 2, 3, 4, or 5 and n′″=0,1, 2, 3, 4, or 5, wherein Ar₁ and Ar₂ are each independently a5-membered heteroaromatic ring; a 6-membered aromatic ring; or a6-membered heteroaromatic ring, wherein Ar₃ is a 5-memberedheteroaromatic ring; a 6-membered aromatic ring; or a 6-memberedheteroaromatic ring, wherein each of Ar₁ and Ar₂ are optionallyindependently substituted with one or more H, alkyl group, alkoxy group,aryl group, which groups may be optionally independently substitutedwith one or more sulfonium, selenonium, or iodonium groups; other acid-or radical-generating species; or monomer or pre-polymer groups, whereinAr₃ is optionally substituted with one or more H, acceptor group, alkylgroup, alkoxy group, aryl group, which groups may be optionallyindependently substituted with one or more sulfonium, selenonium, oriodonium groups; other acid- or radical-generating species; or monomeror pre-polymer groups, wherein R₁, R₂, R₃, and R₄ are each independentlyH, alkyl group, aryl group, which groups may be optionally independentlysubstituted with one or more sulfonium, selenonium, or iodonium groups;other acid- or radical-generating species; or monomer or pre-polymergroups, wherein at least one of Ar₁, Ar₂, Ar₃, R₁, R₂, R₃, or R₄ issubstituted with one or more sulfonium, selenonium, or iodonium groups,or other acid- or radical generating groups, wherein Y is an anionselected from the group consisting of F⁻, Cl⁻, Br⁻, I⁻, CN⁻, SO₄ ²⁻, PO₄³⁻, CH₃CO₂ ⁻, CF₃SO₃ ⁻, NO₂ ⁻, NO₃ ⁻, BF₄ ⁻, PF₆ ⁻, SbF₆ ³¹ , AsF₆ ⁻,SbCl₄ ⁻, ClO₃ ⁻, ClO₄ ⁻, and B(aryl)₄ ⁻, where aryl is an aryl groupcontaining 25 or fewer carbon atoms that may be optionally substitutedwith one or more alkyl groups, aryl groups or halogens, wherein z is aninteger equal to the charge of the chromophore portion of the compound,wherein p is an integer equal to the charge on the anion, and wherein qand Q are integers such that the relationship zQ=pq is satisfied. 18.The compound or composition of claim 1, which has the structure:

wherein X is N, n=0, 1, 2, 3, 4, or 5, n′=0, 1, 2, 3, 4 or 5 and n′″=0,1, 2, 3, 4, or 5, wherein Ar₁ and Ar₂ are each independently a5-membered heteroaromatic ring; a 6-membered aromatic ring; or a6-membered heteroaromatic ring, wherein Ar₃ is a 5-memberedheteroaromatic ring; a 6-membered aromatic ring; or a 6-memberedheteroaromatic ring, wherein each of Ar₁ and Ar₂ are optionallyindependently substituted with one or more H, alkyl group, alkoxy group,aryl group, which groups may be optionally independently substitutedwith one or more sulfonium, selenonium, or iodonium groups; other acid-or radical-generating species; or monomer or pre-polymer groups, whereinAr₃ is optionally substituted with one or more H, acceptor group, alkylgroup, alkoxy group, aryl group, which groups may be optionallyindependently substituted with one or more sulfonium, selenonium, oriodonium groups; other acid- or radical-generating species; or monomeror pre-polymer groups, wherein R₁, R₂, R₃, and R₄ are each independentlyH, alkyl group, aryl group, which groups may be optionally independentlysubstituted with one or more sulfonium, selenonium, or iodonium groups;other acid- or radical-generating species; or monomer or pre-polymergroups, wherein at least one of Ar₁, Ar₂, Ar₃, R₁, R₂, R₃, or R₄ issubstituted with one or more sulfonium, selenonium, or iodonium groups,or other acid- or radical generating groups, wherein Y is an anionselected from the group consisting of F⁻, Cl⁻, Br⁻, I⁻, CN⁻, SO₄ ²⁻, PO₄³⁻, CH₃CO₂ ⁻, CF₃SO₃ ⁻, NO₂ ⁻, NO₃ ⁻, BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻, AsF₆ ⁻,SbCl₄ ⁻, ClO₃ ⁻, ClO₄ ⁻, and B(aryl)₄ ⁻, where aryl is an aryl groupcontaining 25 or fewer carbon atoms that may be optionally substitutedwith one or more alkyl groups, aryl groups or halogens, wherein z is aninteger equal to the charge of the chromophore portion of the compound,wherein p is an integer equal to the charge on the anion, and wherein qand Q are integers such that the relationship zQ=pq is satisfied. 19.The compound or composition of claim 1, wherein said chromophore andsaid generator are each present in concentrations of 0.001 M to 2 M. 20.The compound or composition of claim 1, wherein said chromophore is ananion.
 21. The compound or composition of claim 1, further comprising atleast one polymerizable or cross-linkable monomer, oligomer, orprepolymer, or acid-modifiable medium.
 22. The compound or compositionof claim 1, wherein the chromophore is a molecule having a structureselected from the group consisting of D-π-D, D-A-D, A-π-A and A-D-A,where D is an electron donor and A is an electron acceptor.
 23. A methodfor making an article, comprising: contacting the compound orcomposition of claim 1 with at least one polymerizable or cross-linkablemonomer, oligomer, or prepolymer, or acid-modifiable medium; irradiatingsaid compound or composition to cause a simultaneous two-photon ormulti-photon absorption in said chomophore; and polymerizing saidmonomer, oligomer, or prepolymer or cleaving a group from saidacid-modifiable medium.
 24. An article, produced by the method of claim23.
 25. A method for generating a Bronsted or Lewis acid and/or radical,comprising irradiating said compound or composition of claim 1 to causea simultaneous two-photon or multi-photon absorption in said chomophore.26. A compound or composition, comprising: a first means forsimultaneously absorbing two or more photons; a second means forproducing an electronically excited state upon simultaneous absorptionof two or more photons; and a third means for generating a Bronsted orLewis acid and/or radical upon reaction with said excited state; whereinsaid third means comprises at least one sulfonium, selenonium, oriodonium group, or other acid- or radical generating group.
 27. Thecompound or composition of claim 26, wherein said first and second meansare comprised within a single molecule.
 28. The compound or compositionof claim 26, wherein said first, second and third means are comprisedwithin a single molecule.
 29. An apparatus, comprising: a compound orcomposition, comprising: a first means for simultaneously absorbing twoor more photons; a second means for producing an electronically excitedstate upon simultaneous absorption of two or more photons; and a thirdmeans for generating a Bronsted or Lewis acid and/or radical uponreaction with said excited state; wherein said third means comprises atleast one sulfonium, selenonium, or iodonium group, or other acid- orradical-generating group; and a means for irradiating said compound orcomposition.
 30. The apparatus of claim 29, wherein said means forirradiating comprises one or more laser beams.
 31. The apparatus ofclaim 30, wherein said one or more laser beams are pulsed laser beams.32. A compound or composition, which has the structure:

wherein X is N, n=0, 1, 2, 3, 4 or 5, n′=0, 1, 2, 3, 4, or 5 and n′″=0,1, 2, 3, 4, or 5, wherein Ar₁ and Ar₂ are each independently a5-membered heteroaromatic ring; a 6-membered aromatic ring; or a6-membered heteroaromatic ring, wherein Ar₃ is a 5-memberedheteroaromatic ring; a 6-membered aromatic ring; or a 6-memberedheteroaromatic ring, wherein each of Ar₁ and Ar₂ are optionallyindependently substituted with one or more H, alkyl, alkoxy, aryl,thioalkoxy, thioaryloxy, selenoalkoxy, or selenoaryloxy groups, whichgroups may be optionally independently substituted with monomer orpre-polymer groups, wherein Ar₃ is optionally independently substitutedwith one or more H, acceptor, alkyl, alkoxy, aryl, thioalkoxy,thioaryloxy selenoalkoxy, or selenoaryloxy groups, which groups may beoptionally independently substituted with monomer or pre-polymer groups,wherein R₁, R₂, R₃, and R₄ are each independently H, alkyl, or arylgroups, which groups may be optionally independently substituted withone or more thioalkoxy, thioaryloxy selenoalkoxy, selenoaryloxy orgroups, and wherein at least one of Ar₁, Ar₂, Ar₃, R₁, R₂, R₃, or R₄ issubstituted with one or more thioalkoxy, thioaryloxy selenoalkoxy,selenoaryloxy groups.
 33. The compound or composition of claim 32,wherein the thioether fragment has the formula—(CH₂)_(γ)—(CH₄H₄)_(δ)—SR_(a5), wherein R_(a5) is an alkyl group, andwherein γ=0 to 25, and δ=0 to
 5. 34. The compound or composition ofclaim 32, wherein the thioether fragment has the formula—(CH₂)_(γ)—(C₆H₄)_(δ)—SR_(a5), wherein R_(a5) is an aryl group, andwherein γ=0 to 25, and δ=0 to
 5. 35. The compound or composition ofclaim 32, wherein the selenoether fragment has the formula—(CH₂)_(γ)—(C₆H₄)_(δ)—SeR_(a5), wherein R_(a5) is an alkyl group, andwherein γ=0 to 25, and δ=0 to
 5. 36. The compound or composition ofclaim 32, wherein the selenoether fragment has the formula—(CH₂)_(γ)(C₆H₄)_(δ)—SeR_(a5), wherein R_(a5) is an aryl group, andwherein γ=to 25, and δ=0 to
 5. 37. A composition of a form selected fromthe group consisting of:

wherein R is methyl or benzyl, and wherein X is F⁻, Cl⁻, Br⁻, I⁻, CN⁻,SO₄ ²⁻, PO₄ ³⁻, CH₃CO₂ ⁻, CF₃SO₃ ⁻, NO₂ ⁻, NO₃ ⁻, BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻,AsF₆ ⁻, SbCl₄ ⁻, ClO₃ ⁻, ClO₄ ⁻, or B(aryl)₄ ⁻, where aryl is an arylgroup containing 25 or fewer carbon atoms that may be optionallysubstituted with one or more alkyl groups, aryl groups or halogens.